-... ..
~
._.,...,
------------------------------~?
~~
~2
~~
..'"'.,
2
~
..
~~
~~·
~:-
-,
~·
~=-
l"V!
V'
"~
_-..."
' \.'"
, .
"
. ·,..,
"
Part I
PHYSICAL
AND ·CHEMICAL
.
PRINCIPLES
•
Physical and Chemical Principles
General Inorganic Chemistry
A. GENERAL INORGANIC CHEMISTRY
Table o Common Names o Chemical Com ounds
COMMON NAMES
Alum
Aqua fortis
Aqua regia
Baking Soda
Bleaching powder
Blue vitriol
Borax
Borazon
Butter of antimony
Calcite or Limestone
Calomel
Carborundum
Caustic potash
Caustic Soda, Lye
Chalcocite
Chalcopyrite
Chile saltpeter
Common table salt
Copperas
Corundum
Cream of tartar
Cryolite
Dioxidane
Do lomite
Epsom Salt
Fluorite
Galena
Glauber's Salt
Gypsum
Hematite
Laughing Gas
Limewater
Litharge
Lunar caustic
:v!agnesia or periclase
:v!agnesia Alba
:v!agnesite
:v!agnetite
:v!ilk of magnesia
:v!ohr's salt
:v!uriate of potash
:v!uriatic acid
_-orbide
Oesper's salt
8il of vitriol
CHEMICAL NAME
Potassium aluminum sulfate
dodecalr)'drate
itric acid
Mixture of HCI and HN0 3
Sodium hydrogen carbonate
Calcium hypochlorite
Copper sulfate pentahydrate
Sodium tetraborate decahydrate
Boron nitride
Antimony (III) chloride
Calcium carbonate
Mercurous chloride
Silicon carbide
Potassium hydroxide
Sodium hydroxide
Copper (I) sulfide
Copper ferrous sulfide
Sodium nitrate
Sodium chloride
Ferrous sulfate heptahydrate
Aluminum oxide
Potassium bitartrate
Aluminum sodium fluoride
Hydrogen peroxide
Calcium magnesium carbonate
Magnesium sulfate heptahydrate
Calcium fluoride
Lead sulfide
Sodium sulfate decahydrate
Calcium sulfate dihydrate
Iron (III) oxide Dinitrogen oxide
Calcium hydroxide solution
Lead oxide
Silver nitrate
Magnesium oxide
Basic magnesium carbonate
Magnesium carbonate
Iron (II,III) Oxide
Magnesium hydroxide
Iron (II) ammonium sulfate
Potassium chloride
Hydrochloric acid
Boron carbide
Iron (II) ethylenediamine sulfate
Sulfuric acid
FOR.'\fULA
KAl(S04)2 · 12H20
HN03
3HC1: 1HN03
NaHC0 3
Ca(CI0) 2
CuS0 4 · 5H 20
Na3B40 1· 1OH20
BN
SbC13(aql
CaC03
Hg2C'2
SiC
KOH
Na OH
Cu2S
CuFeS 2
Na 0 3
NaCl
FeS0 4·7H20
A'203
KHC,Ji40 6
AlF3JNaF
H20 2
Ca0Mg02C02
MgS0 4 7H 20
CaF 2
PbS
Na2S04 · 1OH20
CaS0 4 · 2H 20
Fe20 3
N10
Ca(OH)2(aql
PbO
Ag 03
MgO
M~(OH)2(C03)3 · 5H20
MgC03
Fe304 or FeO·Fe20 3
Mg(OH)2<aql
Fe(NH4)2(S04)2·6H20
KC!
HCl
B4C
Fe(en)(S0 4)2 · 4H 20
H2S04 (ag)
Physical and Chemical Principles
Cff\L'lON NAMES
Oleum, fuming sulfuric
acid or ordhausen acid
Paris green
Phosgene
Phospine
Pitchblende
Plaster of Paris
I- Potash
Prussian blue
Prussic acid
.}. Pyrite
Pyrolusite
..,. Quartz, White Sand
J... Quicklime or Lime
. A. Quicksilver
Real gar
Rochelle 's Salt
~ Ruti le or anatase
Salammoniac
" Saltpeter
Si lane
~
Slaked lime
Soda Ash
>- Sugar of lead
Tartar Emetic
Trona
Tumbull's blue
Venetian sublimate
Washing Soda
Witherite
General Inorganic Chemistry
CIIEMICAL NA.1\fE
FORMULA
Pyrosulfuric acid
Cupric aceto-arsenite
Carbon oxychloride
Phosphorus trihydride
Uranium oxide
Calcium sulfate hemihydrate
Potassium carbonate
Ferric ferrocyanide
Hydrocyanic acid
Iron sulfide
Manganese dioxide
Silicon dioxide
Calcium oxide
Mercury
Arsenic disulfide
Sodium potassium tartrate
Titanium dioxide
Ammonium chloride
Potassium nitrate
Silicon hydride
Calcium hydroxide
Sodium carbonate
Lead acetate
Antimony! potassium tartrate
Sodium sesquicarbonate
Ferrous ferricyanide
Mercuric chloride
Sodium carbonate decahydrate
Barium carbonate
H2S201
Cu( C2H302)23Cu(As02)2
COCl 2
PH3
U30s
CaS0 4·YiH 20
K2C03
Fe4[Fe(CN)6h
HCN
FeS 2
Mn0 2
Si0 2
Cao
Hg
As2S2
NaKC4H406
Ti0 2
N~Cl
KN03
SiH4
Ca(OH) 2
N a2C03
Pb(CH3C00)2
(SbO)KC4H406
Na3(C03)(HC0 3)·2H 20
. Fe3[Fe(CN)6h
Hg Ch
Na2C0 3·10H20
BaC0 3
The Atomic Theory
Dalton's Atomic Theory
John Dalton (English chemist, mathematician and philosopher)
l.
2.
3.
Elements are composed of tiny indivisible particles called atoms. Atoms of
different elements are chemically different; however, atoms of a given element
are of the same size, shape, mass and chemical properties.
*If two elements combine to form more than one compound, the ratio of the
mass of an element to a fixed mass of the other element is a whole number or a
simple fraction
**A chemical reaction only involves separation, combination or rearrangement
of atoms
* Law of Multiple Proportions
**Law of Conservation of Mass
Law of Definite Proportions states that a pure compound is made up of elements in
the same proportion by mass. (Joseph Louis Proust, French chemist)
2
Physical and Chemical Principles
General Inorganic Chemistry
The Electron
Cathode Ray Tube or Geissler Tube (Sir William Crookes and Heinrich Geissler)
:·is a glass tube with two metal plates connected to a high-voltage source which emitted
'.l ray drawn from the negative plate towards the positive plate. The ray emitted has the
;;ame nature regardless of the material of construction of the glass tube, electrode and the
= used.
Joseph John Thomson (British physicist, recipient of Nobel Prize in Physics in 1906)
etermined the ratio of electric charge to the mass of an electron to be -1.76 x 108
coul/gram .
•~obert Andrews Millikan (American physicist, recipient of Nobel Prize in Physics in
9- 3) determined the charge of an electron to be - 1.60 x 10- 19 coul.
Radioactivity
Ti/helm Konrad.Rontgen (German physicist, recipient of Nobel Prize in Physics in 1901)
discovered the X-rays, which penetrated matter, darkened unexposed photographic plates
and caused metals to emit unusual rays.
Antoine Henri Becquerel (French physicist, recipient of Nobel Prize in Physics in 1903)
discovered radioactivity in uranium.
_\farya Skolodowska Curie (Polish chemist and physicist, recipient of Nobel Prizes in
Physics in 1903 and Chemistry in 1911) discovered radioactivity in uranium and
polonium.
·
Th e Proton and the Nucleus
Ernest Rutherford (New Zealand chemist, recipient of Nobel Prize in Chemistry in 1908)
performed the gold foil experiment wherein a thin foil of gold was bombarded with alpha
particles. He made the follo wing generalizations:
·
1. Most of the atom is an empty space
2. T.he positive charge of an atom is concentrated in the nucleus
The positively charged particle in the nudeus is the proton and carries the same quantity
of charges as an electron. It has a mass of 1.6752 x 10- 24 gram - about 1837 times the
mass of an electron.
The Neutron
James Chadwick (British physicist, rec1p1ent of Nobel Prize in Physics in 1935)
discovered neutron by bombarding a beryllium atom with alpha particles producing an
electrically neutral particle having a mass slightly greater than that of a proton.
Charge and Mass of Subatomic Particles
MASS (gram)
1.67495 x 10-24
Neutron
1.67252 x 10-24
Proton
9.1095 x 10-28
Electron
CHARGE (coulomb)
0
1.6022 x 10- 19
-1.6022 x 10 19
Atomic number is the number of protons in the nucleus of an atom. An atom 1s
electrically neutral _where the number of protons is equal to the number of electrons.
Mass number is the total number of protons and neutrons in th~ nucleus of an atom.
Isotopes are atoms that have the same atomic number but different mass number.
Average atomic mass of an element is the weighted average of the atomic masses of the
isotopes based on their percentage abundance.
3
Physical and Chemical Principles
General Inorganic Chemistry
The Quantum Numbers
I.
2.
3.
4.
Principal Quantum Number (n) pertains to the average distance of the electron
from the nucleus in a particular orbital. It has integral values 1, 2, etc.
Azimuthal/Angular Momentum Quantum Number (!) tells the shape of the orbital.
It has values from 0 to n-1
Magnetic Quantum Nu~ber (mi) describes the orientation of orbitals in space. Its
allowable values are -l to 0 to +l ·
Spin Quantum Number (ms) shows the spin of electrons. Its values are +Yi
(clockwise) and-Yi (counter clockwise)
Electronic Structure of Atoms
Rules and Principles in Writing Electronic Configuration
l. Aujbau Principle - the orbitals of an atom must be filled up in increasing energy
levels.
2. Pauli 's Exclusion Principle - no two electrons in an atom can have the same set of
quantum numbers and an atomic orbital must contain a maximum of two electrons
with opposite spins (Wolfgang Pauli, Austrian physicist, recipient of Nobel Prize
in Physics in 1945).
·
3. Hund 's Rule of Multiplicity- the most stable arrangement of electrons in subshells
is the one with more parallel spins (Frederick Hund, German physicist).
Periodic Table of Elements
• In 1829, Johann Wolfgang Dobereiner, German chemist, arranged the elements in
triads like Li-Na- K, Ca-Sr-Ba, and Cl-Br-I.
• In 1864, John AR Newlands, English chemist, arranged the elements in atomic mass
and found out that every eight element has similar properties.
• In 1869, Russian chemist Dmitri Ivanovich Mendeleev and German chemist Julius
Lotbar Meyer arranged the elements in the periodic table according to their recurring
periodic properties.
• In 1913, a young English ph sici t. Henry GHJn-Jeffreys Moseley discovered the
relationship between the elements ' atomic number and the frequency of X-rays
generated by bombarding the element with high-energy electrons.
Modern Periodic Law - the properties of the elements are functions of their atomic
numbers.
Some Atomic Properties
l. Atomic Size (A tomic Radius) is the average distance between the nucleus and the
valence electron.
2. Ionization Energy is the energy required to remove an electron from a gaseous
atom in its ground state. The lower the IE, the easier it is for an atom to form a
cation.
3. Electron Affinity is the change in energy when an electron is accepted by a gaseous
atom to form an anion.
4. Electronegativity is the measure of the ability of an atom to attract towards itself a
bonding electron.
4
Physical and Chemical Principles
General Inorganic Chemistry
The Electronegativities of Common Elements
Linus Carl Pauling (American chemist, recipient of Nobel Prize in Chemistry in 1954
and Nobel Peace Prize in 1962)
-
-
H
2.1
Li
Be
B
c
N
0
F
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Na
Mg
Al
Si
p
s
0.9
1.2
1.5
1.8
2.1
2.5
K
Ca
0.8
1.0
..
Cl
3.0
Br
2.8
-
I
-
Variation of Physical Properties in the Periodic Table
Across
Li
B
Na
Down a
group .. .
K
Rb
Cs
Fr
c
ProJ!er~
2.5
-
aperiod . ..
N
Increasing
••
•
Atomic Size
Metallic Property
Reactivity
Ionization Energy
Electmn Affinity
Elec'tronegativit~
~
0
F
Decreasing
"'
"'
••
•
Chemical Bonds
Covalent Bond - results from the attraction of the nucleus and the electron of two or
more atoms and usually involves two non-metals
Ionic Bond - results from the attraction of two opposite charged particles and involves a
metal and a non-metal
Properties of a Chemical Bond
1. Bond Energy is the amount of energy involved in the formation and breaking of a
bond.
2. Bond Length is the distance between the nuclei of the atoms forming the bond.
3. Bond Order pertains to single bond, double bond, triple bond and those
intermediate between single and double bonds, etc.
Theories of Bonding
!. Valence Bond Theory - the formation of a bond is due to the overlap of two
atomic orbitals.
2. Molecular Orbital Theory - a bond is formed when electrons in the bonding
molecular orbital is greater than the electrons in the non-bonding molecular
orbital.
5
General Inorganic Chemistry
Ph. ical and Chemical Principles
Jfolecular Geometry
GEOMETRY
linear
trigonal planar
bent
tetrahedral
trigonal pyramid
bent
linear
trigonal bipyrarnid
see-saw
T-shaped
linear
octahedral
square pyramid
square planar
pentagonal bipyramid
pentagonal pyramid
TYPE
AB1
AB3
AB 2E
AB4
AB3E
AB2E2
ABE3
ABs
AB 4E
AB3E2
AB3E3
AB6
ABsE
AB4E2
AB1
AB6E
BOND ANGLE{S}
180°
120°
less than 120°
109.5°
107°
104.5°
180°
90°, 120°,180°
90°, 120°, 180°
90° 180°
' .
180°
90°,180°
<90°, 180°
90°,180°
72°,90°
72°,90°
HYBRIDIZATION
sp
sp2
sp2
sp3
sp3
sp3
SJ23
dsp 3
dsp 3
dsp 3
dsp 3
d2sp3
d2sp3
d2sp3
d3sp3
d3sp3
Chemical Reactions
1. Combination Reaction (Synthesis) : A+ B ~AB
a. metal + oxygen gas -+ basic oxide or basic anhydride
0
2Mg + 0 2 -+ 2Mg0
b. non-metal + oxygen gas -+ acidic oxide or acidic anhydride
0
S + 0 2 -+ S02
c. non-metal oxide + water -+ acid
a
C02 + H20 -+ H2C03(aq)
d. metal oxide + water -+ alkali/base
0
MgO + H 20 -+ Mg(OH)2
2. Decomposition : AB -+ A + B
a. metal oxide
6.
metal - oxygen gas
Hg+ Yi0 2 (Joseph Priestley, 1774)
b. metal carbonates -6 ~ metal oxide + CO
a
HgO -
6- -
--~
Na20 + C02
6
c. metal nitrates -6 ~ metal nitrites + 0 2
a2C03
0
c
...
-a.:-0 3
aN02 + Yi02
~
d. metal bicarbonates
-..i~
-~aHC03 ~
e. metal oxyhalides
0
6
metal carbonate + H 20 + C0 2
a2C03 + H20 + C02
metal halide + 0 2
2KBr0 3 -------~ 2KBr + 302
L\ I Mn02 I Fe203
3. Single Replacement: AB+ C-+ CB+ A
a. Hydrogen Displacement Reactions
0
Na + H 20oJ -+ NaOH + YiH 2cgJ
0
2Fe + 3H20(v) -+ Fe203 + 3H2(g)
0
Zn + 2HClcaqJ -+ ZnCJi + H2Cgl
b. Halogen Displacement (Activity Series : F2 > Ch > Br2 > Ii)
0
2KI + Cl2 -7 2KC1 + I2
6
EXAMPLE
C02
BF3
S02
CH4
NH3
H20
CH30PC1 5
Sf4
CIF3
XeF2
SF6
BrF 5
Xef4
lF7
TeC16- 2
Physical and Chemical Principles
General Inorganic Chemistry
4. Double Decomposition (Metathesis)
a. Neutralization Reaction - reaction of an acid and a base forming salt and water
a
HCl +KOH ---7 KC!+ H 2 0
b. Precipitation Reaction - reaction which results in the formation of an insoluble
product
0
a1C03cav + CaS04Cav ---7 CaC03Csl + Na2S04(aq)
A ctivity Series of Metals
arranged in decreasing activity)
B 0 8@!1 Eil GQ B ~~El El~ [B-.
I
I
~
DISPLACE .H YDROGEN FROM ACIDS
DISPLACE HYDROGEN FROM STEAM
D ISPLACE AYDROGEN
FROM COLD WATER
Colligative Properties of Solutions of Non-Electrolytes
l.
Boiling Point Elevation (BPE):
where
m = molality,
BPE = TB,solution - TB,solvent = K 9 m
K 8 = ebullioscopic constant
2. Freezing Point Depression (FPD) : FPD =T F,solvent -TF,solution = KFm
where
KF
= cryoscopic constant
3.
Vapor Pressure Lowering (VPL) : VPL = p
4.
Osmotic Pressure (1t):
1! =
solvent
- P
solution
=X
solute
P
solvent
MRT where: M =Molarity, R = 0.08205 L-atm/K-mol
Crvoscovic and Ebullioscovic Constants.of Common Solvents
SOLVENT
KB
KF
SOLVENT
KB
KF
Water
Benzene
Acetic acid
0.52
1.86
-
37. 7
2.57
5.12
1.20
-
3.07
3.90
Camphor
Ethanol
Methanol
0.80
-
Chemical Equilibrium
,....onsider the hypothetical reaction: aA(g) + bBcgJ =+ cC(g) + dDcg)
?or gases and aqueous solutions in a chemical reaction, equilibrium constants are
=xpressed in terms of molarity (Kc) and partial pressure (Kp) as follows:
K
c
= [Cr[D]ct and K = [Pc nPo]d
[A]"[B]b
P
[PA)"[Ps] b
-:Oese cases apply for ideal solutions and ideal gases where the activities are estimated to
~ the concentrations in molarity and partial pressures for gaseous species.
7'efationship between Kc and Kp
Kp = K c (RT)l'illgases
where: Lin gases= 2:ngas,product - 2:ngas,reactant = (c + d )- (a+ b)
7
Physical and Chemical Principles
General Inorganic Chemistry
s Pri ciple
_. .ibrium when subjected to a stress will act in such a way to relieve
Lill = - 45 kJ/mol
!::+ 2 NH 3cgl
.gino 1he Concentration
.
d reasing) the concentration of the, reactants shifts the reaction forward
___,_.,,._,,._,,.,..;.In reasing (decreasing) the concentration of the products shifts the reaction
1 ~-l~~
~re orward). In the given reaction, removing NH 3 in the reaction vessel shifts the
forward wh ile adding some NH 3 shifts the reaction backward.
~~~·'" ::
~
-_-
s of Changing the Pressure/ Volume
In reasing the pressure (or similarly decreasing the volume) of a system in
equilibrium shifts the reaction towards the formation of less number of gaseous
molecules. On the other hand, decreasing the pressure. (or similarly increasing the
\'Olume) of a system in equilibrium shifts the reaction towards the formation of greater
number of gaseous molecules. In the reaction given above, increasing the pressure of the
system will result in the formation of more ammonia.
Effects of Changing the Temperature
Increasing the temperature favors an endothermic reaction while decreasing the
temperature favors. an exothermic reaction. For the reaction above, mcreasmg the
temperature will favor the backward reaction being exothermic.
Effects ofAdding the Catalyst
Adding a catalyst does not affect the equilibrium.
Nuclear Chemistry
Types of Emitted Particle/Radiation
PARTICLE
CHARGE
beta particle or electron
-1
positron
+l
op
or _o
e
1
1
op or +le
o
+I
proton or a l;tydrogen nucleus
+l
+1POr+1H
neutron
0
on
gamma ray
0
gy
alpha particle or helium nucleus
+2
+ia or +iHe
Ways of Expressing Quantity of Radiation
1.
Activity - number of nuclear disintegrations per second
a.
b.
c.
2.
SI Unit : Bq
3.7 x 10 10 Bq (becquerel) = 1 Ci (curie)
Curie is the rate of disintegration of 1 gram of Ra
Radiation absorbed dose (rd)
a. SI Unit : Gy (gray)
b. 1 Gy = I J/kg absorbing material
c. I rd= 10-5 J/gram of tissue
8
SYMBOL
_
I
I
I
-• ical and Chemical Principles
General Inorganic Chemistry
-sf.cal Constants
Symbol
Constants
- ed of light
:>mruttivity of free space
_ tron charge
:-..tomic mass unit
:> anck' s constant
educed Planck's constant
£0
e
u
h
Ii
E ectron rest mass
m,
Value
2.99792458 x
8.854187817 x
1.602176487 x
1.660538782 x
6.62606896 x
1.05457163 x
9.10938215 x
5 .48579911 x
1.672621637 x
1.007276467 x
1.674927211 x
1.00.8 664916 x
1.097373157 x
3.645068202 x
7.297352538 x
c
oton rest mass
-eutron rest mass
"Rydberg constant
Balmer constant
:Cine-structure constant
Dimension
108
1o- 12
10-19
m-s 1
F-m- I
10~27
kg
J-s
J-s
kg
u
kg
u
kg
u
cm- 1
m
[]
1o-34
34
1031
. 1010-4
10- 27
10°
27
10[ 0°
10 5
10-7
10- 3
c
Balancing Nuclear Reactions
Conservation of Mass Number
The total number of protons plus neutrons in the products and in the reactants must
be the same
Conservation of Atomic Number
The total number of nuclear charges in the products and in the reactants must be the
same
Types of Radioactive Decay
Alpha Particle (a particle)
0
basically a helium nucleus
0
commonly found during radioactive decay from heavier nuclide
0
net result is to increase the neutron to proton ratio
2
J!Po
-+
84
proton
neutron
nip
2
JiPb
+
iHe
82
134
132
1.595
1.610
Beta Particle(~ particle)
0
basically an electron
0
the symbol -~ e represents an electron in or from an atomic orbital
0
the symbol
0
other electron, comes from the nucleus and not from an atomic orbital
emitted when the neutron to proton ratio is higher than the zone of stability (a
neutron is transformed to a proton and an electron)
_ffJ
represents an electron ~hat, although physically identical to any
s2 P b
214
-+
g3 Bz. + -1O/J
214
I
on
-+
3. Gamma Ray (y ray)
0
Also known as high energy photon
0
Usually a by-product of an alpha particle decay
238
234 .
4
0
92 Pb-+ 90 Bz+ 2 He+2 0 y
9
I
0
1P
+-le
General Inorganic Chemistry
1 Principles
• on (e}
= •.\n antimatter of electron emitted when the neutron to proton ratio is lower than
the zone of stability (a proton is transformed to a neutron) ·
io
1
-+
iN
1
+ ~e
{p
-+
Jn + ~e
Electron Capture
0
Inner orbital electron is captured by the nucleus to increase neutron to proton
ratio
0
Usually accompanied by emission of gamma ray
JlAs
proton
neutron
nip
-+
84
134
1.595
]{Ge
+
iHe
82
132
1.610
Nuclear Stability
1. Strong Nuclear Force
0
force of attraction present between nucleons (proton and rteutrons) over an
extremely short distance of about 1 x 10- 15 m
0
overcomes electromagnetic forces over short distances
2. Properties of the Neutron
0
serves as a nuclear binder of neighboring protons despite the electric repulsion of
positive charges but only over short distances
0
At large distances, strong nuclear force become less significant that is, the more
protons (heavier nucleus) in the nucleus, the more neutrons are needed to hold
them together
0
Smaller atomic nuclei usually have the same number of protons as neutrons
0
A single neutron is rather unstable and will convert itself to a proton and an
electron
3. Radioactive Decay and Nuclear Stability
0
process where heavier nucleus loses nucleons to yield smaller but more stable
nucleus
0
when a nuclide has 84 or more protons, it tends to be unstable and undergo
radioactive decay
0
stable nuclides have neutron to proton ratio equal to one while unstable nuclides
have neutron to proton ratio greater than one
0
nuclides with even number of protons and neutrons are more stable
Protons
Odd
Odd
Even
Even
Neutrons
Odd
Even
Odd
Even
-+ Arranged in increasing stability -+
0
beta emission can lower neutron to proton ratio while positron em1ss1on or
electron capture increase neutron to proton ratio
nuclei that contain 2, 8, 20, 50, 82, or 126 protons or neutrons are generally more
stable than nuclei that do not possess these numbers
0
10
p:
4.
Physical and Chemical Principles
General Inorganic Chemistry
4. Binding Energy
0
The amount of energy released during a nuclear transformation and is a measure
of the energy used to bind the nucleons in a parent nuclide
~Ebind = ~c
2
0
Mass defect (~) is the change in mass during a nuclear transformation
0
The higher the binding energy per nucleon implies more mass is converted to
pure energy.to bind the nucleons and hence the more stable the nuclei is
Fe-26 is the most stable nuclei where nuclei ·with lesser mass number needs to
break up (fission) to achieve maximum stability while those with greater mass
number needs to combine (fusion) to achieve maximum stability
~m = mproducts - mreactants
°
REVIEW QUESTIONS AND PROBLEMS
1. Arrange the proton, neutron and electron in increasing mass.
a. proton < electron < neutron
c. electron < neutron < proton
b. electron < proton < neutron
d. neutron < electron < proton
2. The constant known as the fundamental number of hydrogen is the _ __ __
a. Rydberg constant
c. Fine-structure constant
b. Planck's constant
d. Balmer constant
3. In Rutherford's experiment, which of the following is true?
a. the proton is evenly distributed in the nucleus of an atom
b. the atom is almost an empty space
c. the nucleus contains proton, neutron and electron
d. all of the these
4. The ~um of the number of protons, neutrons and electrons of a zinc ion, Zn~2 is
a. 94
b. 92
c. 95
d. 93
5. The region in space where an electron is most likely to be found is called
a. orbital
b. energy level
c. shell
d. nucleus
For numbers 6 and 7...
Calculate the series limits for the following:
6. Balmer series (m = 2)
a. 4389 cm- 1
b. 27434 cm- 1
Brackett series (m
a. 4389 cm- 1
=
c. 12193 cm- 1
d. 6859 cm- 1
c.12193cm- 1
d. 6859 cm- 1
4)
b. 27434 cm- 1
8. Atoms with the same atomic number but different mass number is called _ _ __
a. isobars
b. isotopes
· c. isotherms
d. isoelectronic
9. The quantum number that has an allowable value ofO, 1, 2, etc. is the
a. Magnetic Quantum Number
c. Angular Momentum Quantµm Number
b. Spin Quantum Number
d. Principal Quantum Number
11
General Inorganic Chemistry
emical Principles
;: - umbers I 0 and 11 .. .
Calculate the minimum wavelength of light necessary to overcome the work
functions for the following metals:
10. Li (cp = 2.90 eV)
a. 248 nm ·
b. 428 nm
c. 575 nm
d. 581 nm
11. Ge (cp = 5.00 eV)
a. 248 nm
b. 428 nm
c. 575 nm
d. 581 nm
12. It states that no two atoms will have the same set of quantum numbers.
a. Heisenberg Uncertainty Principle
c. Aufau Building Up Principle
b. Pauli ' s Exclusion Principle
d. Hund 's Rule of Multiplicity
13. What is the speed of an electron being emitted by Rb (cp = 2.16 eV) when 350 nm of
light shined on the metal in the vacuum?
a. 1.87 x 10 5 mis
b. 4.60 x 10 5 mis
c. 7.00 x 105 mis
d. 9.94 x 105 mis
14. What is the maximum number of electrons in an atom that can have the quantum
number: n= 2, ms= -Yi ?
a. 8
b. 6
c. I
d. 4
15. The atomic weight of chlorine is 35.45 and its naturally occurring isotopes are Cl-35
and Cl-37. What is the percentage abundance ofCl-35?
·
a. 95.8%
b. 98 .7%
c. 77.5%
d. 75.0%
16. Which of the following properties do not depend on the electronic configuration of
the atoms?
a. physical
c. nuclear
b. chemical
d. none of the above
17. Which of the following sets of quantum numbers is incorrect?
a. n=l, l=O, mF-1, ms= -Yi
c. n=3, /=l, mFO, ms= - Yi
b. n= I, l=O, mFO, ms= +Yi
d. n=4, /=2, mF -1, ms= +Yi
18. In what group of the periodic table is the element with the following electron
configuration? [Ar] 4s 2 3d 10 4p 3
a. IA
b. 2A
c. 3A
d. 5A
19. Which of the following pairs are isoelectronic?
a. Mn+2 and Ar
b. zn+2 and Cu+2
c.
s·2 and er'
d. Na+ and
er'
20. The change-in energy when an electron is accepted by a gaseous atom to form an
anion.
a. Electronegativity
c. Ionization Energy
b. Electron Affinity
d. Activation Energy
Which of the following halogens is the most electronegative?
a. F
b. Cl
c. Br
d. I
g the members of the Chalcogen Family, which is the most non-metallic?
- =::!fur
b. Selenium
c. Tellurium
d. Oxygen
\
I
g
2
12
Physical and Chemical Principles
General Inorganic Chemistry
_3. Arrange the fo llowi ng in increasing ionization energy:
a
Mg
B
C
1
2
3
4
a. 415 32
b. 51432
c. 23415
N
5
d. 23514
24. The ·theory that states that bonding is caused by overlapping of two atomic orbitals.
a. Va lence Bond Theory
c. Vital Force Theory
b. Molecular Orbital Theory
d. Valence Shell Electron-Pair Repulsion
25. It pertains to si ngle bond, double bond, triple bood and those intermediate between
single and double bonds, etc.
a. Bond Order
b. Bond Length
c. Bond Strength
d. Bond Degree
26. Which of the following molecules/compounds is formed by covalent bonds?
a. LiF
b. MgO
c. ZnS
d. BeC12
27. A compound whose molecules are not associated by hydrogen bonding is
b. (CH 3) 2NH
c. HCOOH
d. (CH 3) 3COCH 3
a. CH 3CH 20H
_8. Type of equilibrium that exists between similar phases is called
a. physical equilibria
c. chemical equilibria
d. heterogeneous equilibria
.b. homogeneous equilibria
_9. Which of the follo wing equilibrium system will have its Kr equa l to its Kc?
c. H 2<gl + h <gl !:::+ 2HI<gl
a. 2 NO<gl + Br2(gJ !:::+ 2NOBr<gl
b. COcgl + C'2cgl !:::+ COC'2c~l
d. N 2cgJ + 3H 2cgJ !:::+ 2NH3cgJ
30. Consider the reactio'n: PCl 5(g) !:::+ PCl3(g) + C'2(g)
Afi 0 rxn = 87 .9 kJ/mol
Which of the foll ow ing will result in the increase in concentration of Cl 2 gas?
c. add PCl 5
a. add PC13
b. cool the mixture
d. increase the pressure
3 1. Consider the follo wing reaction at l 600°C: Br2(gl !:::+ 2Br(gl·
When 1.05 moles of Br2 are placed in a 2 L flask, 2.50% of Br2 undergoes
dissociation. Calculate the Kr for the reaction .
a. 0.206 89
b. 0.001346
c. 3.7216
d. 0.0953
32.
aC10 2 is
a. sodium chloride
b. sodium hypochlorite
c. sodium chlorite
d. sodium chlorate
33 . oxalic acid + sodium hydroxide -+
a. Na2C0 3
b. NaC 2H302
+ H20
c. NaCHO
d. Na2C 20 4
34. Which of the following is an acidic oxide?
a. MgO
b. S02
c. N a20
d. Cao
35. Which of the fo llowing substances in aq ueous solution of the same concentration
will have the highest boiling point elevation?
a. KC!
b. Na 2S0 4
c. CH 3COOH
d. NaCl
36. The vapor pressure of water at 25 °C is 23.756 torr. A solution consisting of 18.913
grams of a non-volatile substance in 36 grams of water has a vapor pressure of·
20.324 torr. What is the molecular weight of the solute?
b. 56
c. 48
d. 39
a. 62
13
General Inorganic Chemistry
o \\1
-.
- 1 6. ~
·ac
urea, (NH 2 ) 2 CO solution in water?
c. -9.18°C
d. -l l.77°C
- ezing point of a 0.205 molal solution with respect to urea (60
of this solution is diluted with 250 grams of water?
b. -O. l 72°C
c. --O. l 74°C
d. --O. l 76°C
·- pressure of a dilute aqueous ethyl alcohol solution at 25 °C is 38 mmHg.
boiling point elevation of this solution.
b. 0.0025°C
c. 0.0041 °C
d. 0.0011 °C
o.oo.,8°C
,,-~ the
,, ___ 6 decays by alpha emission. What is its decay product?
?8
a. ·p,7 Fr
b.
22?
. ?30
8(, Rn
c. - 90f'h
d.
2
~~Ac
The half-life of 90 Sr is 29 years. What fraction of the atoms in a sample of 90 Sr would
remain 100 years later?
a. 0.29
b. 0.14
c. 0.18
d. 0.09
42. A sample of radioactive material was found to be 90% disintegrated after 50 years.
What is the half-life of the material?
a. 7.5 yrs
b. 8.7 yrs
c. 15.l yrs
d. 22.2 yrs
For numbers 43 and 44 .. .
Radium-226, which undergoes alpha decay, has a half-life of 1600 years.
43. How many alpha particles are emitted in 10 min by 10 mg sample of radium-226?
Assume one year to have 365 days.
a. 1.1 x 10 11
b. 2.2 x 10 11
c. 3.3 x 10 11
d. 4.4 x 10 11
44. What is the activity of the sample in mCi? (!Ci= 3.7 x 10 10 disintegration/s)
a. 7.9 mCi
b. 8.9 mCi
c. 9.9 mCi
d. 10.9 mCi
45. If
238
92 U
undergoes decay and found to pro duce ?34B
-90 z· , what other particle was
emitted?
a. alpha
b. gamma
c. positron
d. electron
46. Potassium-40 decays to argon-40 with a half-life of 1.27 x 109 years. What is the age
of the rock in which the mass ratio of 40Ar to 4°K is 4?
a. 1.4 x 109 years
b. 2.9 x 10 9 years
c. 4.2 x 10 9 years
d. none of these
47. It is equivalent to the rate of disintegration of 1 gram of radium
a. becquerels
b. curie
c. gray
d. rem
48. Which of the following particles cannot be accelerated in a particle accelerator?
a. alpha
b. e1ectron
c. neutron
d. proton
49. What is the binding energy per nucleon for C-13 ( 13.003355 amu) in MeV?
a. 4.5
b. 5.5
c. 6.5
d. 7.5
50. Starting with 1.000 gram of Sr-90, 0.953 gram will remain after 2 years. Calculate
the initial activity ofSr-90 in Ci? 1 Curie (Ci) = 3.70 x 10 10 disintegration/sec
a. 70
b. 140
c.210
d. 280
14
n
ti
J
Physical and Chemical Principles
Organic Chemistry
B. ORGANIC CHEMISTRY
Organic Chemistry - branch of chemistry that deals with compounds of carbon
History of Organic Chemistry
Vital Force Theory
Organic compounds originated from living materials, either plants or animals. Such
materials possess vital force and compounds that are extremely difficult to synthesize in
he laboratory.
Friedrich Wohler
He synthesized urea in the laboratory from the inorganic compound, ammonium
cyanate. Ure'ii is a component of urine, and thereby ending the concept ofvitalism.
NH4CNO ~ (NH2\co
Structural Theory
1.
2.
Atoms in an organic compound have fixed number of bonds. This combining
ability is termed as valence.
Carbon can form bonds with another carbon atom accounting for a high
percentage of carbon in most organic compounds. Tbis ability of carbon 1s
called catenation .
Chemical Bonding
Dualism (Berzelius)
Atoms are being held by electrical attraction ·between species of opposite charge.
_\toms form bonds to completely fill their valence shells. There are two ways by which
::.n atom bonds with another atom:
1. by gaining or losing electrons forming ionic bond
2. sharing of electrons with another atom forming covalent bond
Ionic Bond
Atoms with high ionization energy tend to lose electrons easily while atoms with low
affinity tend to gain electrons easily.
~.ectron
Covalent Bond
Atoms forming covalent bonds share electrons to acquire the configuration of the
- ble gases (octet rule) . Hydrogen acquires the electron configuration of the noble gas
-elium.
rormal Charge= group number- Yi shared e- - number of unshared e. ·riting Lewis Structures
1.
2.
3.
4.
5.
Determine the total number of valence electrons of all atoms (also equal to their
group· number)= n
Determine the total number of electrons for each atom that will satisfy the octet
rule= m
The number of bonding electrons is m - n
The number of electron - pair bonds is Yi (m- n)
Assign the correct formal charge for each atom
onance Theory
A molecule or an ion represented in two or more Lewis structures that differ only in
· -e positions of electrons exhibit the property of resonance. These structures are called
:.sonating structures or resonating contributors.
15
Physical and Chemical Principles
Organic Chemistry
Classification of Organic Compounds
l. Hydrocarbons - compounds containing carbon and hydrogen
a. Aliphatic - compounds whose carbon atoms are arranged in chains whether
straight or branched
0
Alkanes (CnH2nd - contain single bonds
0
Alkenes (CnB 2n) - contain double bonds
0
Alkynes (CnH 2 n-2) - contain triple bonds
0
Alkadienes (CnH 2n_2) - contain two double bonds
b. Alicyclic - compounds containing carbon atoms in a ring system
° Cycloalkanes (CnH 2n) - alkanes arranged in the form of a closed chain
° Cycloalkenes (CnHzn-z) - non-conjugated alkenes in a ring system
c. Aromatic - compounds containing carbon atoms with conjugated double bonds in
a ring system
2. Hydrocarbon Derivatives (classified according to heteroatoms present)
a. Derivatives containing Oxygen
0
Alcohols (R-OH) and Phenols (Ar-OH) - hydrocarbons with one or more
hydrogen atom replaced by -OH group
0
Ethers (ROF.) - hydrocarbon derivatives with two hydrocarbon groups
attached to oxygen
0
Epoxides - cyclic ethers in which the oxygen is included in a three-membered
ring
0
Aldehydes (RCHO) and Ketones (RCOR) - hydrocarbons with one or two
alkyl groups attached to C=O
° Carboxylic Acids (RCOOH) - hydrocarbons with the carboxyl group, - .
COOH
0
Esters (RCOOR) - carboxylic acid derivatives with the hydrogen atom
replaced by an alkyl group
0
Acid Anhydride - carboxylic acid derivatives with the hydrogen atom
replaced by RC=O
b. Derivatives containing Halogens
0
Alkyl Halides and Aryl Halides - hydrocarbons with the hydrogen atom
replaced by one or more halogens
c. Derivatives containing Sulfur
0
Thiols - hydrocarbon derivatives with hydrogen atom replaced with -SH
0
Disulfides - hydrocarbon derivatives with general formula R-S-S-R
d. Derivatives containing Nitrogen
'
0
Amides - carboxylic acid derivatives with hydrogen atom replaced with H2, -NHR', -NR' R"
0
·Amine - organic derivative ofNH3
AL KAN ES
• General Formula: CnH2n+2
• also called paraffins
3
• contains sp hybridized carbon
Source of Alkanes - obtained from fractional distillation of petroleum
Physical Properties of Alkanes
1.
Physical State at Room Temperature
C1 - C4 gases
Cs - C 17 liquids
C 1s - Cn solids
16
Organic Chemistry
Physical and Chemical Principles
2.
3.
Solubility
c
practically insoluble in water due to non-polar character and inability to form
hydrogen bonds while soluble in benzene, chloroform and carbon
tetrachloride
Boiling Point
c
increases as length of carbon chain increases and decreases due to branching
Nomenclature of Alkanes
1. Choose the longest continuous carbon chain and the parent name 1s named
according to the number of carbon present.
CH 3
I
I
H,
HJC .......... 2 /CH
3
CH
'
4
/~'-
c
H,
I
6
" CH3
'
CH 3
- hexane
Number the chain in such a way that the substituents present are assigned with the
lowest number.
CH-
CH-
I,
I
I,
H3C ...._ 2 ,.......c H..._ 4 ,.......c H..._ 6
3 ' c
5
" c
' c H3
H1
H1
incorrect numbering
For identical substituents present more than once, the carbon numbers for which
the substituents are attached and the prefixes di, tri, tetra, etc. are written before
the name of the substituents.
For two identical substituents, the number is used twice
attached before the name of the substituent.
/
.
H3~ ...........
CH 3
5
ii
I
H3C ........... 4 /c........._ 2 /
c
Hi
c
4
C/
I
CH3 H1
the prefix di is
CH3
H,C
H1
CH3
~nd
~I
C-
I
2
/
C
CH3
I
H,
CH2
H3C
3,3 - diethylpentane
3,3 - dimethylpentane
For two or more different alkyl substituents, names are \Yri-en in alphabetical
order giving no consideration on the prefixes.
/
CH3
7
•
H3C...._
6
H2
I
I
,_..CH...._ 4 / CH
5
3
CH
"c'
CH3
H,C
I
I
2
.;CH;
' c....H"
CH 3
3 - ethyl - 4,5 - dirnethylheptane
17
Organic Chemistry
emical Principles
-
Alkrl S uhstituents
_-_nIE
STRUCTURE
H3c - cHi
Ethyl
STRUCTURE
NAM E
-
I
Sec-Butyl
CH
H3C /
'-c Hi
CHi
I,
CH-
Hi
,........c,
Propyl
HiC
) so butyl
Hi C- -
CH
HiC/ ' - c -Hi
H,
HiC ............
HC- -
Isopropyl
Butyl
HiC /
/C~
Hi<:;
CH3
H3c - c - -
Neopentyl
CH3
Br
I
CH..._
'CHi
!.Mg in dry ether
2.H 30 +
--~---~
Hi
2.
Hydrogenation of Alkene
CH3
I
HiC ......... ~C .........
C
CH3
H
3.
Reduction of Alkyl Halide
Br
I·
HiC -....
" c'
Hi
4.
!.Zn
2.HBr
_,..CH
'-cH,
Wurtz Synthesis (Coupling Reaction)
Na in
dryether
)
Reactions of Alkanes
I.
Halogenation
Cli
UV/heat/light
CH3
Br,
UV/heat/light
,
H-c -
c-
CH3
Preparation of Alkanes
1. Grignard Synthesis using Alkyl Halide
Hi e , /
" c
I,
I
CH-
I
I
Tert-Butyl
/H2C C
Hi
H·C
I
I
, ' -c- C- CH3
H,
Br
18
c -Hi .
Physical and Chemical Principles
2.
Organic Chemistry
Combustion
3
< n+ll/2
CnH2n+2 +
02
-7
nC02 + (n+ 1) H20
ALKEN ES
• General Formula: C 0 H2 0
• also called olejins
• contains sp 2 hybridized carbon
.Vomenclature ofAlkenes
..
1. Select the longest parent carbon chain containing the double bond. The parent
carbon chain is named like alkanes but.the ending used is "ene".
eH 3
13
H2
H3e, 2 b e , 4 / e , 6
5
C~
e
eH3
I
I
H2
eH3
- hexene
2. Lowest number is assigned for the carbon bearing the double bond.
eH,
I
H,e,
2
"'e
CH3
I.
be:....
I
~
H2
4 ,.......c, 6
5 "'eH"'e
H2
'
I.
H2
H3e......_ 5 be, 3 ,.......e, I
2 "'cH
"'e ~ "'e
3
H2
6
I
eH,
CH3
correct numbering
incorrect numbering
3. Substituents are named and numbered just the same with alkanes.
CH 3
I,
H2
H3C ' 2 b e ,4 / c , 6
5
e~
C
eH3
H2
I
I
eH 3
2,3 - dimethyl - 2 - hexene
eparation ofAlkenes
1. Dehydration of Alcohol
I,
CH·
,......cH . . . _ ,......CH,
H3C
Hp• , heat
CH
I
OH
Dehydrogenation of Alkyl Halides
I,
CH·
CH
H3c/
/
' cH
CH3
KOH, EtOH
)
I
Br
5aitsev's Rule - the alkene formed is the one that is more alkyl substituted
19
Physical and Chemical Principles
Organic Chemistry
3. Debrornination of Dibromides
Br
I
H3C"
/ CH '-
H3C
/
CH
CH 3
_ /H
/ c(E)c"'-
Zn
I
Br
H
CH 3
Reactions of Alkenes
l. Hydrogenation
I, I
I I
H
. CHH3C"
/H
c= c
H3C
"' -
/
,
H,
i/Pi!Pd
,
H-C-C-C-CHH
H
CH3
alkane
Halogenation
2.
CH 3
H3C"
'
_ /H
/ c- c"'-
H3C •
Cl
I I
Cl 2
inCC1 4
H3C - , - , - CH3
H
Cl
CH3
vicinal dihalide
3.
Addition ofHX
I, I
CHH3C"
HiC
_ /H
c- c
"'
/
HX
H
H3C- , - , - CH3
X=Cl,Br,l
x
CH3
H
alkyl halide
Markovnikoff's Rule, "The halogen attaches to the carbon that is more alkyl substituted
thus producing a higher order alkyl halide."
Anti-Markovnikojf's Addition of HBr in the presence of Organic Peroxides
H-C -
'
HBr
CH-
H
C-
C-
H
Br
I, I
I I
CH-
,
lower order alkyl halide
4.
Hydroxylation
H3C'-
H
" c= c/
H3C
/
"'
cold, dilute, neutral
KMn04
CH3
H3C -
CH-
H
C-
C-CH3
OH
OH
I, I
I I·
diol
CH3
H
I I
I I
H3C-C-C-CH3
OH
diol
20
OH
Physical and Chemical Principles
Organic Chemistry
5. Ozonolysis
0
HiC'/
"'
-
c-
H,c
/
1.03
2. Zn, H 2 0
c"-
0
IIc
H
HJC /
CH3
'
IIc
+
CH3
HJC/
ketone
'H
aldehyde
0
IIc
1.03
2. Zn, H 2 0
HiC /
0
IIc
+
'CH,
H/ '
H
aldehyde
ketone
6. Oxidation
0
1.KMnO,,Ho·
2.heat
3.H 3 0+
IIc
+
H3C /
'
OH
carboxylic acid
l.K.Mn0 4 , H02. heat
3.H 3 0 +
+
HiC -
CH 3
H
C-
C-
I
I
CH 3
I I
OH
H
alcohol
8.
Oxymercuration-Demercuration
I.Hg(CH 3COOJi!fHF-H 2 0
2. NaBH,' Ho-
CH 3
H
c-
C-
I I
I
H,c -
1
OH
H
alcohol
9.
Hydroboration-Oxidation
H3C'-
H
/
/ "'c-- c"-
H3c
l.THF-BH 3
2.H 20 2 , HO-
H,c -
CH3
CH-
H
c-
C-
H
OH
I, I
1
I
CH -
,
alcohol
0.
Halohydrin Formation
X 2 in H10
X=Clor Br
H,c -
CH-
H
c -
C-
OH
X
I, I
1
I
halohydrin
Water attaches to carbon with more alkyl substituent
ALKYNES
• General Formula: CnH2n-2
• also called acetylenes
• contains sp hybridized carbon
21
CH-
,
CH-
,
Physical and Chemical Principles
Organic Chemistry
Preparation of Alkynes
1.
Reaction of Sodium Acetylide with Alkyl Halides
aNH,
+
+
2.
Dehydrohalogenation of Vicinal Dihalides ·
Br
I
/CH'H3C
/ CH 3
CH
I
Br
3.
Dehalogenation of Tetrahalides
Br
Br
I I
tt.c- c - c - c t t.
, I I ,
Br
2Zn
)
Br
Reactions of Alkynes
I.
Hydrogenation
H
H
I I
H3C - 1 - 1 - CH3
2H,
Ni, Pt or Pd
H
H
alkane
H
H,
Pd(Pb
Lindlar's Cataly
_
H
"-.
/
/ c(i)c'-.
H3C
CH3
cis-alkene
H
H2
a or Li in
NH 3 orC 2 H 5 NH~
low temp
"-
/CH3
/CWC"
H3C
H
trans-alkene
2.
Halogenation
x
x
I I
H3C - 1 - 1 - CH3
2X 2
X=BrorCI
x x
tetrahalide
3.
Addition ofHX
X
H
X
H
I I
H,C-C-CH
, I I
2HX
X=BrorCI
geminal dihalide
Follows Markovnikoff's Rule
22
NaBr
Physical and Chemical Principles
4.
Organic Chemistry
Hydration
OH
,
H-C -
I_
C-
H-C -
tautomerism
H
C-
CH
H
enol
5.
H
II I
,
I
keto-enol
I
CH
0
ketone
Oxidation
0
0
IIc
H3C/
'
+
OH
II
HO -
C-
OH
carbonic acid
carboxylic acid
0
H3c- c= cH
IIc
I. KMn0 4 , HO' ,heat
2.H 3 0 +
H3C /
'
OH
+
carboxylic acid
AROMATIC COMPOUNDS
• compounds containing benzene ring and behaves chemically like benzene
• compounds that are planar, cyclic and follows Huckel 's Rule
Huckel's Rule
4n + 2 =
7t
electrons, where n must be a whole number
.Vomenclature of Aromatic Compounds
Jtfonosubstituted Benzene
1.
ame the substituent followed by the name "benzene".
2. IUPAC recognizes common name of monosubstituted benzene as follows:
o-~-H
Acetophenone
Anisole
Aniline
o-~-OH
Benzaldehyde
O c=N Q-c!CH3 0-0H
•
Benzo1c Acid
Benzomtnle
Styrene
Toluene
\ CH3
Cumene
Phenol
Disubstituted Benzene
3. The ring is numbered to give the lowest number for the substituents present.
o~-,,,
·O ~-rn,
correctly numbered
incorrectly numbered
23
Physical and Chemical Principles
4.
The prefixes ortho-, meta- and para- are also used to denote 1,2, 1,3 and 1,4
positions of the substituents, respectively. If common names are to be used as
parent name, the second substituent is numbered such that number 1 is assigned to
the carbon bearing the substituent of the parent compouncL
·0-~=rn, 5
Organic Chemistry
•O ,=rn,
m-chlorostyrene
p -chlorostyrene
o-chlorostyrene
D'1sub st1tute
.
db enzenes wit common names are given as fio II ows:
6'"' Ct, ¢ 6 '"' 6 "' ¢
OH
OH
OH
CH,
CH3
o-xy,ene ,
m-xy ene
p-xy ene
o-creso
m-creso
OH
OH
COOH
COOH
OH
6 °" 6 ¢
6'~
bH
OH
pyrocathecol
resorcinol
hydroquinone .
phthalic acid
p-creso
COOH
6,~
¢
isophthalic acid
terephthaltc
acid
COOH
Polysubstituted Benzene
6. The ring is numbered to give the lowest number for the substituents present. If a
parent compound is present, number 1 is assigned to the carbon to which the
functional group of the parent compound is attached.
·-0-°"
3
·- 0'"
s
'.!
incorrectly numbered
5-chloro-4-fluorophenol
correctly numbered
3-chloro-4-fluorophenol
Source and Properties of Benzene
•
•
•
•
•
•
obtained from catalytic dehydrogenation of cyclohexane and from coal tars
stabilized by delocal ization of 7t electrons
all C-H bonds are equivalent
.
does not decolorize KMn0 4
H 2 does not add even in the presence of a metal catalyst
undergoes substitution reaction
Reactions of Benzene
1. Halogenation
0
6
x,
(X=Clor Br)
AICl 3 or FeBr3
halobenzene
24
Physical and Chemical Principles
Organic Chemistry
Nitration
.0
2.
nitrobenzene
Sulfonation
0
3.
o~-OH
ti
fuming
H 2 S0 4
0
benzenesulfonic acid
Friedel-Crafts Alkylation
0
4.
6
HN0 3
B ,so .
6
R-X
AICI 3
alkyl benzene
Friedel-Crafts Acylation
0
0
II
+
()'' ·
AICI-
aromatic ketone
Reactions of Monosubstituted Benzenes
5.
-0
Oxidation of Alkylbenzenes
OR
I
II
I. KMn0 4 , HO' ,heat
2.H 3 0 +
(J'' o
benzoic acid
6.
Conversion of Benzenesulfonic Acid
o~-OH
M
7.
NaOH
fuse
phenol
Reduction ofNitrobenzene
O NO,
0-0H.
2
o-N
H
Fe, HCI
aniline
8.
Preparation. ofDiazonium Salts
0-NH,
HNOi, low temp
Ot=N
diazonium salt
25
+
C02
Physical and Chemical Principles
Organic Chemistry
- ·o - of Diazonium Salts
O+·=·
O t=N
O t=
O t=N
O t=N
O t=N
O CI
O s,
Cu 2 CI ,, heat
N2
+
chlorobenzene
Cu 2 Br,, heat
N2
+
bromobenzene
Kl, heat
0-1
)
N2
+
iodobenzene
O c=N
O OH
OH
Cu , (CN),, heat
N2
+
benzonitril~
H, O
)
+
N2
N2
+
phenol
H3 PO,
+
H3P03
benzene
Effects of Substituents
- a monosubstituted be~ene can undergo substitution reactions depending on the
substituent initially present
Ortho-Para Directors
Strongly Activating
H
-
R
I
\H
N
-
R
I
\H
N
-
I
\R
N
-OH
Moderately Activating
-C
-CH -N
-C
-R
0
0
II
H
II
3
H
-
Weakly Activating
-R
Weakly Deactivating
-
F
-
CI
-Br
26
-I
0 -R
-
o
Physical and Chemical Principles
Organic Chemistry
Meta Directors
Moderately Deactivating
0
II
II
0
0
0
II
-C-OH
-S-OH
II
-C-OR
0
0
II
II
-C-H
-C-R
Strongly Deactivating
R
II°
-+
~
F
I
-N-R
1+
Cl
-C-F
- C - Cl
R
F
0
I
I
I
I
Cl
ALCOHOLS AND ETHERS
Alcohols
• contain the functional group -OH (hydroxyl group)
_Vomenclature of Alcohols
I.
Alcohols are named as alkanol. The alkane is named and the "e" is dropped and
replaced by "ol".
·
The substituents ·are numbered with the hydroxyl group given the priority in
numbering.
CH3
I
OH
H,
, _..C..._ 3
H3c'
I
.s ....,.CH
OH
; / CH
Hc ~ ' 'rn
CH
' "c/ 2 '-rn,
H2
I
2-pentanol
3
OH
I
I
2
'-cH.
I'
.s
Hc/
)
I
CH
OH
3
I
CH
' ' cH_.... 2 '-cH.
I
I'
OH
CH3
3,4 - dimethyl-2- pentanol
2,3,4 - pentanetriol
Ethers
• contain the functional group -OR (alkoxy group)
Nomenclature of Ethers
1.
Ethers can be named by simply naming the substituent to the oxygen atom in
alphabetical order followed by the word "ether" .
CH3
H,
C
H3c/
I
CH
'-...o/
'-cH 3
ethyl isopropyl ether
2.
ethyl methyl ether
methyl propyl ether
For complicated ethers, the -OR group is named as an alkoxy substituent to the
longest parent carbon chain of the alkane.
CH;
H,
C
H3c/
I
CH
'-...o/
'-cH,
2-ethoxypropane
methoxyethane
1-methoxypropane
l-methoxy-3-methylcyclohexane
27
Physical and Chemical Principles
Organic Chemistry
Physical Properties ofAlcohols and Ethers
1.
2.
Boiling Point
- alcohols have higher boiling points compared to ethers due to hydrogen bonding
Solubility in Water
- solubility decreases as chain length increases
Preparation of Alcohols
1.
Acid- Catalyzed Hydration of Alkenes
H3C'
H
/c=c(
H,C
2.
l.H. , H,O
)
CH3
Oxymercuration- Demercuration
H3C''- _
CH3
H
/
/c-c"-.
H,C
H
I I
I I
l.Hg(CH 3COO)iffHF-H 20
2.NaBH 4 ,Ho·
H 3c - c - c - c t t .
CH3
OH
CH-
H
H
I, I
l.THF-BH 3
2.H,0 2 ,HO.
4.
H,c-c-C-CH-
1
I
H
OH
,
Reduction of Carbonyl Compounds
0
/
H, c ,
IIC"'-
LiAIH,
OH
C
carboxylic acid
0
H3C'
II
C
/C'-
LiAIH 4
+
)
OCH3
H1
ester
OH
0
H3C'
C
II
/
C"'-
H,c ...._
LiAIH 4 or NaBH 4
I
'c
CH3
/CH
'-cH 3
Hi
H.
ketone
2° alcohol
0
H C'
3
II
/C'-.
C
Hi
H
LiAIH 4 or NaBH 4
HiC' / C " ' )
C
Hi
H2
1° alcohol
aldehyde
28
OH
,
Physical and Chemical Principles
5.
Organic Chemistry
Using Grignard Reagent and Organolithium Compounds
OH
0
II
/c,
H3C'
·
C
H1
I
I
H3C - C - C - CH3
RMgX orRLi
H1
CH3
.,5' t',(l\
R
ketone
3° alcohol
0
OH
I
II
/ c,
H3C '
C
H1
H3C '
RMgX orRLi
/CH
'R
C
H1
H
aldehyde
2° alcohol
OH
0
IIc
RMgXorRLi
/
)
H/'H
I
CH
'R
H
methanal
1° alcohol
H1
0
/\
RMgXorRLi
H1C-CH2
)
epoxide
/ C ' /OH
R
C
H1
1° alcohol
Reactions of Alcohols
1.
Conversion to Alkyl Halides
CH 3
H
I I
I I
H1C - c · - C - CH·
OH
,
HX
H,c -
Hl>HBr>HCl
H
3°>2°> 1°>methyl
29
CH·
H
c -
C-
I, I
I HI
X
CH3
Organic Chemistry
and Chemical Principles
2.
Oxidation to Carbonyl Compounds
Non
I,
CH ·
1.
..,..CH
KMnO,
H.c ....-
/
OH
'-c
,
HO- 1 H 2 0 ,heat
II
0
1° alcohol
carboxylic acid
CH 3
I
CH
PCC
CH 2 Cl 2 , heat
H
c/
H
' c/
,
II
0
1° alcohol
aldehyde
I,
CH·
..,..CH
,
H·C '
/
' IIc
CH 3
0
ketone
2.
Preparation of Ethers
1.
Dehydration of Alcohols (Preparation of Symmetrical Ethers)
H1S0 4
I40°C
2° alcohol
2.
Williamson Synthesis (Preparation of Unsymmetrical Ethers)
I,
CH ·
CH
H 3C /
' -oH
alcohol
I,
CH·
H,
CH
+
'-cJNit
sodium alkoxide
H3C /
c·
""- x
H3c /
1° or methyl halide
p
Reaction of Ethers
Acid Cleavage
HX
(X =l,Br)
lower order ROH
ALDEHYDES AND KETONES
• contains the carbonyl group
R
\ c= o
I
R
\=o
I
H
-.
\ c=
I
o
R
al ehy e
30
ketone
Organic Chemistry
Physical and Chemical Principles
Nomenclature of Aldehydes and Ketones
1.
Aldehydes are named as alkanal. The alkane is named and the "e" is dropped and
replaced by "al". The terminal carbon bearing oxygen is given number 1. For
aldehydes in which the -CHO group is attached to the ring, the suffix carbaldehyde
is used.
0
II
H,
r ,. . .~c,
' / CH , 2
,
H·C
H,~/~'-.~/~ '-. H
3
1
I
CH
•
H
CH,
2,3-dimethylpentanal
butanal
cyclohexane carbaldehyde
0
( Y c'-
v
II
"''tr'~"
H
3-methylbenzene carbaldehyde
benzene carbaldehyde
2.
0
,
II
Ketones are named by naming the alkyl or aryl group attached to the carbon bearing
the oxygen atom. For complicated ketones, the longest parent carbon chain is named
as an alkane, the ending "e" is dropped and replaced by "one". The carbon bearing
the oxygen atom is given the lowest number.
CH,
I
H,
Hc/~'-.~/~H '-CH
J'
I J
II
0
2-methyl-3-pentanone
(ethyl isopropyl ketone)
0
0
II
II
H,C/~'-.~/~H,
I
H,
H3C/~'-.t/c;:,~H3
Hi
I
H2
2-pentanone
(methyl propyl ketone)
bu tan one
(ethyl methyl ketone)
")o
1-(4-methylphenyl)-2-propanone
( 1-methylcyclohexyl)-ethanone
Physical Properties of Aldehydes and Ketones
1. Boiling Point
- intermediate between alkanes and alcohols of the same molecular weight
2. Solubility in Water
- due to high polarity, aldehydes and ketones are soluble in water
Preparation of Aldehydes and Ketones
Aldehydes
1. Oxidation of Primary Alcohols
CH 3
I .
CH
PCC
CH 2 Cl 2 , heat
H1c
/
'e". . .
II
0
1° alcohol
aldehyde
31
H
Organic Chemistry
Physical and Chemical Principles
2.
.
Reduction of Acy! Chlorides, Esters and Nitriles
I,
CH
H
,c /
I
Cl
CH
I . LiAIH(O-t-butyl)
2.H,O
' c/
II
H
,c /
H
'c/
II
0
0
acyl chloride
aldehyde
CH 3
CH 3
I
...,CH
,
H C.r
}
CH 3
CH-
I
...-O-CH 3
CH
l . D!BAL-H
2.H 2 0
'c'
II
H
c/
H
'c/
,
II
0
0
ester
aldehyde
CH 3
I
CH
H
H C/
'c/
l.DIBAL-H
2.H,O
,
II
0
aldehyde
Ketones
· 3. Ozonolysis of Alkenes
I,
CH-
/C~/CH3
H3C
c
II
2.Zn, H,O
C
H
0
ketone
alkene
4.
H' /
c
H 3C ' /CH 3
·1.0,
+
CH 3
II
0
aldehyde
Friedel-Crafts Acylation
0
+
benzene
aromatic ketone
- 5.
Oxidation of Secondary Alcohols
H,
/
H 3C
c:...._
/CH 3
CH
I
PCC
CH,CJ ,, heat
OH
2° alcohol
6.
From Nitril.es using Grignard or Organolithium Reagent
RMgXorRli
)
nitrile
32
Physical and Chemical Principles
Organic Chemistry
Reactions ofAldehydes and Ketones
.Vucleophilic Addition
1.
Addition ofHCN
c
I
I
H3c-
HCN
c-
c-
cH 3
H,
OH
cyanohydrin
HC
cyanohydrin
2.
Addition of Grignard Reagent or Organolithium Compounds
OH
H3c -
RMgXorRLi
I
cH,
cl - CH3
R
ketone
3° alcohol
0
OH
IIC' -
H3C'-.. /
C
RMgXorRLi
H3C'-.. /
C
)
· H
I
CH
'-R
Hi
aldehyde
3.
2° alcohol
Addition of Alcohols
0
H
/0-H
/c".
H3C"
II
/c,
ROH
H.. or RO"
H,C" /OR
HJC"
IIc
ROH
H.. or RO-
'-..CH3
HJC
ROH
/ c".
H.. or RO"
HJC
OR
hemiacetal
ketone
Addition of a Primary Amine
H·C
'\
c=
I
H3C
o
' \ c=
I
H,C
+
1mme
Addition of Hydroxyl Amine
H
H~
\
I
H
\
c=
o
+
/
N-
OH
~
H
hydroxylamine
oxime
33
OR
acetal
Addition of Ammonia and Derivatives
H·C
OR
acetal
/ 0-H
/ c".
0
4.
H
hemiacetal
ald~hyde
H3C /
/c".
H+ or RO-
OR
H
"CH 3
HJC" /OR
ROH
- H
Organic Chemistry
Physical and Chemical Principles
Addition of Hydrazine (Woljf-Kishner Reduction)
H3C
'\
H ·C
, '\
c=
I
H,_ -
+
o
NH_,
HO-
hydrazine
H3c
/
~
c=
-
NH2
H3c
hydrazone
--0#
Addition-.of Phenylhydrazine
H;C'\
I
c=
H,N -
+
o
-
H;C
H
..
~
phenylhydrazine
phenylhydrazone
Addition of 2,4-Dinitrophenylhydrazine
'\
c=
I
"'"-,--0-
H·C
,
o
+
o,
o,
H 3C
phenylhydrazine
2,4dinitrophenylhydrazone
5. Oxidation of Aldehydes and Ketones
Oxidatiqn ofAldehydes
H-C
'\
c=
I
H
' '\
c=o
I
HO
H·C
,
+
o
carboxylic acid
Baeyer-Villiger Oxidation ofAldehydes and Ketones
0
II
/
H 3C
C .......... /
0
OH
ethaneperoxoic
acid
0
v
II
0
II
/C ..........
~c ........_
CH3
·e yde
H>
+
H 3C
/OH
0
ethaneperoxoic
acid
phenylethanoatr
eny. > 3 alkyl> 2° alkyl> 1° alkyl> methyl
CARBOXYLIC ACID AND DERIVATIVES
Carboxylic Acid
• contains the functional group -COOH (carboxyl group)
Carboxylic Acid Derivatives
• obtained by replacing the -OH group by chlorine, carboxylate, alkoxy and amino
group
34
hysical and Chemical Principles
Organic Chemistry
. --omenclature of Carboxj;lic Acid and Derivatives
'::arboxylic Acid
Carboxylic acids are named by naming the alkane, dropping the "e" and replaced by
"oic acid". The carboxyl group is assigned number 1.
0
CH 3
I
H,c
,,...-cH
3 '
4
II
0
II
C:' /
I
c ...._
' " oH
H2
H,
lj
/ C~i/'<'-.
1 /0H
2
H-C
'~ C
C
Hie; , , ,,...-c1 ...._
' CH
' OH
';
Cl
3-methylbutanoic acid
2-chloropropanoic acid
..
I
II
CH 3
0
3-methyl-3-pentenoic acid
For dicarboxylic acids, the alkane follo wed by "dioic acid".
0
0
II
HO
/
0
c ......._ /
C
II
OH
II
0
II
HO
HO/~ '-..~ /~ ...........OH
II
H,
/c1 ......._ ,/~......._,/oH
C
H,
'
C
II
Hi
0
ethanedioic acid
(oxalic acid)
0
propanedioic acid
(malonic acid)
butanedioic acid
(succinic acid)
•• cyl Chloride
They are named by naming the carboxylic acid, dropping the "oic acid" and adding
-oyl chloride".
0
II
0
H3
II
c;, , ,,...-c,
'
3-methylbutanoyl chloride
CH
I
Cl
1
((''"
Cl
2-chloropropanoyl chloride
benzoyl chloride
~ter
3..
The alkyl substituent is named first, then the carboxylic is named, the ending "oic
id" is dropped and replaced by "oate".
0
II
II
H,
H,c /3c,~ /~ ...........O4
H,
( ('',,..-'' '";
0
CH3
H2
methyl butanoate
ethyl benzoate
Amide
The carboxylic is named, the ending "oic acid" is dropped and replaced by "amide" .
..\lkyl substituents to the nitrogen atom is named as N-alkyl.
0
IIc
0
II
H,
H
c /3c ,~ /~ .......... NH
',
Hi
I
H,
c·
.......... N /
((
I
CH ,
'-cH
'
CH 3
N-methylbutanamide
N-ethyl-N-methylbenzamide
35
Physical and Chemical Principles
Organic Chemistry
Acid Anhydride
The carboxylic acids are named followed by "anhydride".
0
0
II
(J
II
c, /c'o
CH3
.
benzoic ethanoic anhydride
Preparation of Carboxylic Acid
1.
Oxidation of Alkenes
H
H3C ........... ~~c ........... c /
H
CH3
H3C ........... ~O
c
l.KMn04 , HO- , heat
I
2.H O'
H2
+
OH
carboxylic acid
alkene
2.
carboxylic acid
Oxidation of Alkylbenzenes
0
OI
II
()'' o
R
l.KM n0 4 ,HO",heat
2.H.o +
~
3.
+
benzoic acid
Oxidation of Methylketones (Iodoform Reaction)
0
1.1 2 in aOH
2.H 30-
2-butanone
4.
II
CHh
H,c' -c/ c'-..oH
Hi
+
Iodoform
(yellow precipitate)
propanoic acid
Oxidation of Aldehydes
H·C
'\
c=
I
HO
H·C
'\
c=
I
H
5.
o
+
o
carboxylic acid
Oxidation of Primary Alcohols
I,
CH·
KMn0 4
HO- ,H 1 0,heat
c"
H
J
_...CH
_... OH
'-c,. . .
II
0
1° alcohol
carboxylic acid
36
Physical and Chemical Principles
Organic Chemistry
Reactions of Carboxylic Acid (Preparation of Carboxylic Acid Derivatives)
I,
CH ·
I,
CH·
__..CH
_..... OH
' c'
,
II
H·C '
/CH
PCl1 , PCl 5 or SOCI,
' ·IIc
/
,
H C
Cl
0
0
acyl chloride
I,
CH ·
..,....cH
H3C
'
c
. ,. . .a,
/
II0
pyridine
CH,
C
II0
acid anhydride .
I,
CH ·
/ 9........_
/CH
H3C
'
c
/
CH3
C
II0
II
0
acid anhydride
I,
CH·
__..CH
_... NH2
'c'
He'
'
II
0
amide
CH·
I'
__..CH
He'
J
H
/
' IIc
N-R
0
amide
CH3
"
/
R -N - R
HC
~
J
I
CH
R
' IIc
/
0
amide
· actions of Acyl Chloride
Conversion to Acid Anhydride
CH 3
I
__..CH
H·C '
,
' c'
_.....Cl
II
0
37
I
N-R
P
~
'cal and Chemical Principles
Organic Chemistry
Conversion to Ester
HO'-... /
CH3
c
H1
pyridi ne
3.
Conversion to Amide
H
R
I
R
R
CH-
I,
_..C H
,...Cl
H-c '
"-c '
,
-
R-
Ii.
-
-
R
II
0
Reactions ofCarboxylic Anhydride
H,c ,
c
II
/o'-... /
c
CH3
+NH 4 0--.......... /
II
0
II
+
0
0
acid anhydride
H,c ,
c
/
II
o'-... /
c
ammonium carboxylates
CH3
II0
0
+
acid anhydride
R
H,c ,
c
/
II
0
o'-... /
c
CH3
II
0
R-
J-l,
-
H,c '-...c /
R
c
II
0
/
o'-... /
c
II
I
........_ R
II
acid anhydride
H,c ,
CH 3
c
0
amide
H3C'-... /
c
CH3
OH
II
H,O
0
0
acid anhydride
carboxylic acid
38
+
Physical and Chemical Principles
Organic Chemistry
Reactions of Ester
H,c ........_
c
,. . . . . a,
/
CH3
c
II
H;C .......... /
0
II
H,O
c
+
0
alcohol
carboxylic acid
. ester
H,c ........_
OH
c
H,
,. . . . . a,
/
CH;
, a·o·'-.... /
c
II
CH 3
c
H,
0
II
aOH
+
0
alcohol
carboxyiate
ester
eactions of Amide
H
H 3C .......... /
I
H 3 C .......... /
C
H
II
OH
c
N "'-
II
I.H 3o•
2. H.,O, heat
0
carboxylic acid
0
amide
H
H 3C .......... /
I
H3C ""'-. /
H
II
1.NaOH
2.H 20,heat
II
+
0
carboxylic acid
0
amide
-
OH
c
N "'-
C
INES
• contains the functional group -NH2
• may be considered as derivatives of ammonia with alkyl or aryl substituents
·omenclature of Amines
An amine can be named by naming the substituent in alphabetical order followed by
the word "amine".
H
I
H
H3C .......... /
C
H2
I
N'-..
/
CH 3
CH
I
..........
CH;
CH 3
ethylmethylamine
phenylisopropylamine
ethy ldimethy !amine
For complicated amines, the -NH 2 group is named as an amino substituent.
0
II
H3C '-..
CH
H,
H3C '-. 4 ......... ~ , ,
'
CH
'
CH
,. . . . c,
OH
I
I
NH 2
1
OH
I
Cl
2-aminopropanoic acid
H,
. . . .- c:......
NH 2
2-amino-4-chloropentanol
If an alkyl group is substituted to the amino group, it is named as N-alkylamino
substituent.
H
0
I
II
/ N'-.. ,.......c..._
, . I
H-C
CH
" OH
OH
CH3
I
I
H;C -...
_,..~H
_... N -...
_.... CH;
1
3
' " c'
- '-c '
"'c ..,,...
CH 3
2-(N-methylamino )-propanoic acid
1-(N-ethyl-N-methylamino )-2-butanol
39
P . "cal and Chemical Principles
Organic Chemistry
Physical Properties ofAmines
1. Boiling Point
- primary and secondary amines are capable of hydrogen bonding and boils
much higher than alkanes but lower compared to alcohols of the same
molecular weight
- tertiary amines do not form intermolecular hydrogen bonding and boils at a
lower temperature compared to primary and secondary amines of the same
molecular weight
2. Solubility in Water
- aliphatic amines containing five carbon atoms are soluble in water
- aromatic amines are slightly soluble in water
3. Basicity
- In aqueous solutions, the order of basicity of amines is observed as follows:
Preparation ofAmines
1.
Alkylation of Ammonia
CH -
I,
I,
CH·
/
/
CH..._
2.
/
Cl
H 3C
' c
H 3C
H,
CH ..._
' c
/
NH 2
H,
amine
Reduction of Amides, Nitro Compounds and Nitriles
0
C'
.
H3
c
/
IIC........
H2
/
CH3
LiAIH.,
)
H
amide
CH 3
I
/
H3C
CH '
/
N0 2
LiAIH,,
)
C
Hi
2-methyl- 1-nitropropane
CH 3
v
nitrile
3.
I
~CH
2H 2
Raney Ni
'~;-'"'
amine
Reduction ofNitrobenzene
I. Fe
2. HCI
aniline
aniline
40
Physical and Chemical Principles
Organic Chemistry
Reaction of Amines
1.
Reaction with Strong Acids
HCI
REVIEW QUESTIONS AND PROBLEMS
1. Which of the following contains sp-hybridized carbon?
a. C4Hs
b. C3H6
c. CsH s
Bond formed in the head-on overlap of two orbitals
a. sigma
b. dative
c. pi
d. double
3. Part of a molecule where most of its chemical reactions occur
a. single covalent
c. triple covalent
b. double covalent
d. functional group
4. Which of the following molecules is unsaturated?
~ · CH30H
c. CsH 1o
a. C3Hs
~ /CH3
CH3
HiC
I
I
..,..CH
H
c'
/CH
I
'cH
3
5. Name the alkane
'-cH
3
CH3
a. 2-ethyl-3,4-dimethylpentane
b. 4-ethyl-2,3-dimethylpentane
c. 3,4,5-trimethylhexane
d. 2,3,4-trimethylhexane
6. Which of the following alkanes is gas at room temperature?
a. octane
b. propane
c. e1cosane
d. undecane
7. When ethyl bromide is treated with sodium in dry ether, the product is
a. propane
b. butane
c. methylpropane
d. ethane
8. For the following alkanes, the one with the lowest_boiling point is
CH 3
I
c
a. 3
H3c/l"-cH3
CH 3
(3)
d. can not tell
b.2
9. The following reagents will produce an alkane from an alkyl halide except
a. Zn I H+
b. Na I dry ether
c. alcoholic KOH
d. all of these
10. How many possible monochlorinated product is expected from the chlorination of
propane?
a. 1
b.2
c. 3
d.4
41
Organic Chemistry
Physical and Chemical Principles
11. Name the alkene:
· a. 2-methyl-2-butene
b. 3-methyl-2-butene
c. 1,2-dimethylpropene
d. none of the above
12. The name of the saturated hydrocarbon isomer of cis-3-hexene is _ _ __
c. n-hexane
a. 2-methylpentane
b. 3-methylpentane
cyclohexane
a.
13. For which of the compounds below are cis-trans isomers possible?
CH 3CH=CH 2
CH3CH=CHCH2CH3
CH 3CH=CHCH3
(1)
a. only 2
(2)
b. both 1 and 2
(3)
c. both 2 and 3
d. all of these
14. When l -bromo-2-methylcyelobutane is treated with alcoholic KOH, the dominant
product is
~CH3
r-/CH3
a.LJ ~b.u
15 .. Among the following alcohols, methylpropene can be obtained from
a. 1-butanol
. c. 2-methyl-2-propanol
b. 2-butanol
d. all of these
16. Alkenes are commonly prepared via elimination reaction, which of the following is
not an elimination reaction?
c. Dehalogenation of vicinal dihalide
a. Dehydration of alcohol
b. Dehydrohalogenation of alkyl halide
d. Hydrogenation of alkynes
17. The following reagents will yield an alkyl halide from an alkene except
a. Br2 I uv or light ' b. Br2 in CC4
c. HCI
d. HBr I peroxide
18. The acid-catalyzed addition of water to I-butene will form
a. 1-butanol
c. isopropyl alcohol
b. 2-butanol
d. propanol
19. The rule which states that, "In the addition of HX to alkenes, the halogen attaches to
the doubly bonded carbon with more alkyl substituent."
a. Saitsev's Rule
c. Markovnikoff's Rule
b. Hoffman Rule
d. none of these
20. Starting with 2-methyl-2-butene, which of the following processes must be used to
produce a secondary alcohol?
c. Addition of bromine water
a. Acid-catalyzed hydration
b. Oxymercuration-demercuration
d. Hydroboration-oxidation
21. Which of the following reagents will yield a diol from a given alkene?
a. hot, acidic KMn0 4
c. Os0 4 in NaHS0 4
b. 0 3, Zn and H20
d. H+ I H20
42
Physical and Chemical Principles
Organic Chemistry
_2. Hydrogenation of alkynes in the presence of a poisoned palladium catalyst produces
a. alkane
b. alkyne
c. alcohol
d. alkene
_3. Addition ofHBr to alkynes results in the formation of
a. geminal dihalide
c. tetrahalide
b. vicinal dihalide
d. enol
_.i_
When 2-butyne undergoes ozonolysis, the main product is
a. carbon dioxide
b. acetic acid
c. acetaldehyde
d. acetone
_5. In hydration of alkynes, the enol formed is found .to transform into a ketone. This
form of isomerism is known as - - - - c. keto-enol tautomerism
a. geemetric isomerism
d. positional isomerism
b. structural isomerism
CH 3
I
/c~,.........cH......_
26. Name the alkyne: H3c
c
CH3
a. 4-methyl-2-butyne
b. 2-met~ -butyne
7
c. 2-propynyl-propane
d. none of these
Which of the fcltowing alkynes contain acidic hydrogen?
a. 2-pentyne
~ - 3-pentyne
c. 2-butyne
d. propyne
Among the following molecules, which is not aromatic?
L
b.
co
C.
CCJ
0
d. all of these
_9. All of the following are ortho and para directing substituents except
a.-OH
b.-F
c. - OR
d.-N0 2
:o. How many isomers does xylene have?
a. 1
~ 1.
b. 2
Vinylbenzene is also known as
a. styrene
b. cumene
c. 3 .
d.4
c. mesitylene
d. durene
Which of the following carbonyl compounds produce a secondary alcohol with
LiAIH4?
a. aldehyde
b. ketone
c. ester
d. carboxylic acid
--'· Addition of methyl magnesium bromide to acetaldehyde produces
a. ethanol
b. 1-propanol
c. methanol
d. 2-propanol
Oxidation of isopropyl alcohol with KMn04 will yield
a. acetone
b. acetaldehyde
c. acetic acid
43
d. diethyl ether
Physical and Chemical Principles
35. Which of the following
substitution?
a. 2-methyl-2-propanol
b. 1-propanol
Organic Chemistry
alcohols will undergo bimolecular nucleophillic
c. 2-propanol
d. all of these
36. In Williamson synthesis of methyl isopropyl ether, the alcohol used is
a. methanol
c. n-propyl alcohol
b. isopropyl alcohoi
d. ethanol
37. Acid-catalyzed ring opening of an epoxide '1:Vill result in the formation of a/an
a. monohydric alcohol b. dihydric alcohol c. trihydric alcohol d. enol
38. Which is NOT a physical property of alcohols or phenols?
a. Phenols are generally only slightly soluble in water.
b. The solubilities of normal primary alcohols in water decrease with increasing
molecular weight.
c. The hydioxyl group of an alcohol is non-polar
d.'Due~ hydrogen bonding, boiling points of alcohols are much higher than those
of corres~ing alk~nes
39. Hydrocarbon denvatives used as a main ingredient in automobile antifreeze.
a. Ethylene glycol
c. Propylene
b. Isopropyl alcohol
d. Toluene
40. Which of the following tests will distinguish 1-propanol from 2-propanol?
a. Fehling's Test
b. Tollen's Test
c. Benedict's Test
d. Lucas Test
41. The following reagents will give an alkyl halide from an alcohol except
a. NaCl
b. PBr3
c. PC1 3
d. SOC12
42. Which among the following is a ketone?
a. CH 3COCH 3
b. (CH 3) 2 CHOH
c. CH 30CH 2 CH 3
43. Which of the following processes will yield an aldehyde?
a. Oxidation of alcohols using KMn0 4 in basic medium
b. Oxidation of alcohols using chromic acid
. c. Ozonolysis of alkenes
d. Ozonolysis of alkynes
44. A tertiary alcohol is produced using Grignard Reagent using a/an
a. ketone
b. aldehyde
c. alkyl halide
d. epoxides
45. Carbonyl compounds can be obtained by reduction using the following except
a. ester
b. acyl chloride
c. nitrile •
d. amide
46. Addition of hydrazine to carbonyl compounds produces a/an
a. imine
b. oxime
· c. hydrazone
d. semicarbazone
47. Reduction of alkyl phenyl ketone& to aromatic hydrocarbons done by Wolf-Kishner
Reduction uses
a. Zn(Hg), HCl
b. NH 2NH 2, KOH
c. LiAIH4
d. H2 with Ni or Pt
48. With the same molecular weight, a carboxylic acid will have a/an
boiling
point than an alcohol
b. equal
c. higher
d. no basis
a. lower
44
ysical and Chemical Principles
Organic Chemistry
Acid anhydrides upon hydrolysis yield
a. esters
b. amides
c. carboxylic acid
d. acyl halide
Hexanedioic acid is also known as
a. malonic acid
b. succinic acid
c. glutaric acid
d. adipic acid
'
Reaction of alcohol and a carboxylic acid is known as _ _ _ __
a. saponification
b. neutralization
c. esterification
d. epoxidation
Cl
I
H2
/ c , /c~ .H3C
"'c
~o
H1
ame the acyl halide:
a. butanoyl chloride
b. chlorobutanoic acid
c. propanoyl chloride
d. none of these
~
.. ~ Addition of an alcohol to acyl halides-.produces
a. carboxylic acid
b. ester
c. carboxamide
d. none of these
ame the acidic anhydride:
a. acetic anhydride
b. propanoic anhydride
c. acetic propionic anhydride
d. none of these
Addition of ammonia to acid anhydrides produces
a. carboxylic acid
b. ester
c. amide
d. none of these
H2
/ c ' /o'-....
H3C
C
/CH3
C
II
H2
0
~ 6.
Name the ester:
a. ethyl propanoate
b. propyl ethanoate
c. methyl acetate
d. ethyl acetate
An unknown ester was hydrolyzed with water and acid to produce an acid, X and
alcohol, Y. Oxidation of the alcohol with hot KMn0 4 yielded acid X. Oxidation of
the alcohol produced acetaldehyde. Name the ester.
a. methyl ethanoate
c. methyl propanoate
b. ethyl ethanoate
d. ethyl benzoate
When an ethyl acetate is reduced by LiAIH4 the product is _ _ _ __
a. acetic acid
b. ethanol
c. acetone
d. acetaldehyde
-9. Cyclic esters are known as
a. acetals
b. diglyme
c. lactones
d. osazone
c. n-octyl acetate
d. ethyl butyrate
50. The scent of a banana is due to the ester
a. etbyl formate
b. i-pentyl acetate
45
Physical and Chemical Principles
Analytical Chemistry
C. ANALYTICAL CHEMISTRY
Analytical Chemistry - branch of chemistry that deals with the separation, identification
and composition of matter.
Qualitative Analysis (w.hat is present) - type of analysis that reveals the components of
the sample
Quantitative Analysis (liow much is present) - type of analysis that determines the
amount of components present in a sample
Methods of Analyses
A. Classical Methods
l .· Gravimetric Method - deals with the measurement of the mass of a
substance that is chemically related to the analyte.
2. Volumetric Method - measures the volume of solution necessary to react
completely with the analyte.
B. Modem Methods
1. Spectroscopic Method - measures the electromagnetic radiation produced
by the analyte or its interactions with it.
2. Electroanalytic Method - measures the electrical properties of the analyte
such as current (A), potential (V), resistance (Q), and amount of charge
(coul).
Quantitative Analysis
Gravimetric Method of Analysis
Basic Steps on Precipitation Method
1. Sample is dissolved in an appropriate solvent.
2. A precipitant i used to convert the analyte into a sparingly soluble precipitate.
3. The precipitate i om·ened into a product ofkno\vn composition by a suitable heat
treatment.
4. The percentage of the anal~ e in the sample is calculated using the gravimetric
factor (GF):
% analyte in the -
GF = molar mas of anal_ -re x x analyte
molar mass of pre ipitare y precipitate
Volumetric Methods ofAnalysis
Standard Solution - solution of known conce rration
Standardization - proces~ of determining the on entration of an unknown solution
Primary Standard - a substance of high purity ed for standardization
Characteristics ofa Good Primary Standard
1. High purity and high equivalent weight
2. Stable towards air, high temperature and humidity
3. Soluble in water
Conditions for a Volumetric Analysis
1. The reaction must be rapid and can be represented by a simple balanced equation.
2. The reaction must be complete and no side reaction occurs.
3. An appropriate indicator must be available in order to detect the end point of the
reaction.
46
1
Analytical Chemistry
Physical and Chemical Principles
Types of Titration
l . Direct Titration - the analyte reacts with the standard solution directly
2. Back Titration - an excess standard solution is added and the excess is determined
by the addition of another standard solution
· 3. Replacement Titration - the analyte is converted to a product chemically related to
it and the product of such reaction is titrated with a standard solution
Acid- Base Titration
Concepts of Acids and Bases
LEW IS
Electron-pair
ACID
acce tor
Electron-pair
BASE
donor
.....
o==~~~~~~
~~~~~~~~~==;;==~~~~~~===-
BRONSTED-LOWRY
Proton donor
Proton acceptor
ARRHENIUS
Produces *H 30+ in
solution
Produces **HO- in
solution
* hydronium ion, protonated water or solvated proton
** hydroxide ion
Strength ofAcids and Bases
Ionization Reaction - reaction involving formation of ions
Strong Acids/Bases - completely ionized in solution
HCl + H20 - H30+caq) + CrcaqJ
NaOH + H20 - Na+Caq) + HO-caq)
Weak Acids/Bases - partially ionized in solution
HF + H20 !::; H30+(aq) + F-(aq)
NH3 + H20 !::; NH/(aq) + HO-(aq)
Autoprotolysis of Water
H20 + H20 !::+ H30+(aq) + HO-(aq) Kw = 1 x ](F 14 at 25°C
Strong Acids: HCl, HBr, HI, HCI0 4 , HN0 3, H2S04 (only on the first ionization)
Strong Bases: Bases of Group IA and 2A
Weak Acids: HF, HCN, H2S0 3, H3P0 4 and organic acids
Weak Bases : Ammonia and derivatives
Calculation ofpH
Strong Acids : pH= - log [Cacict]
Strong Bases : pH = 14 +log ln HO- cbase J
Weak Acids: pH =- Ji log [KaCacict ) when Cacfka » 1000
Weak Bases: pH = 14 + Ji log [KbCbase J when cba;{b » 1000
At 25°C:
pH+ pOH
=
14
Hydrolysis of Salts
n.
the
Acid and base reacts to form salt and water. As a general rule, salts coming from weak
acids or weak bases hydrolyze in water, that is, only the strong conjugate hydrolyzes in
water. An acidic salt is formed from the reaction of a strong acid and weak base. A basic
salt results from the reaction of a strong base and a weak acid. Thus, a neutral salt is a
product of the reaction between a strong acid and a strong base.
47
Physical and Chemical Principles
Analytical Chemistry
Hydrolysis Reaction of Salts
Acidic Salt : NH4Cl
NH4+ + H20
+-+
H30 + + NH3
· Basic Salt : NaCN
KH --
Kw
K HCN
pH of Salts
Acidic Salt : pH = 7 -
,Yi log [ ~: 1 ] when
i:
1
»> 1000
Basic Salt : pH = 7 +,Yi log [ Csalt] when Csalt >>>I 000
Ka
KH
•
Buffer Solutions
Solutions that contains weak acid or weak base and its conjugate salt. These solutions
tend to resist changes in pH.
pH of a Buffer Solution
[acidic component] Henderson - Hasslebalch Equation
p H = pK a - Iog
.
'
[basic component]
If Kb is given:
pH = 14 -p K b
-
Iog
[acidic component]
.
[basic component]
Primary Standards for Bases
1. Benzoic Acid, C 6H 5COOH
2. Oxalic Acid, H 2 C2 0 4 "2H20
3.
4.
5.
Potassium Biiodate, KH (10 3) 2
Potassium Hydrogen Phthalate (KHP), C6H 4(COOH)(COOK)
Sulfamic Acid (HS0 3NH 2)
Primary Standards for Acids
1.
2.
3.
4.
Calcium Carbonate, CaC0 3
M ercuric Oxide, HgO
Sodium Carbonate, Na2C0 3
Tris-hydroxymethylaminomethane (THAM), (CH2 0H) 3CNH2
Indicators for Acid-Base Titration
I. Bromocresol Green
./ pH Transition Range : 3.8 - 5.4
./ changes from yellow to blue
./ pK. = 4.66
2. Bromothymol Blue
. ./pH Transition Range: 6.2 - 7.6
./ changes from yellow to blue
./ pK. = 7.10
48
Physical and Chemical Principles
3.
4.
5.
Analytical Chemistry
Methyl Red
./pH Transition Range: 4.2 - 6.3
./ changes from red to yellow
./ pK. = 5.00
Methyl Orange
../'pH Transition Range: 3.1 - 4.4
./ changes from orange to yellow
./ pK. = 3.46
Phenolphthalein
./pH Transition Range: 8.3 - I 0.0
./ changes from colorless to pink
./ pK. = 9.00
Applications of Acid-Base Titration
Kjeldahl Method (Determination of Organic Nitrogen)
Step I. Digestion
• The sample is oxidized in hot, concentrated sulfuric acid, H2S04 and turns black . . .
To convert ... Carbon and Hy drogen
to ... C0 2 and H 2 0
To convert ... Amides and Amines
to . .. NH4 +
To convert ... Azo, Azo.xy and Nitro Group
t~ . .. Nor its oxide
• Catalysts
Potassium Sulfate (K2S0 4) - increases the boiling point of sulfuric acid
Mercuric Oxide (HgO) - increases the rate of reaction
Se/enious Acid (H2Se0 3) - best catalyst
Step 2. Distillation
• The oxidized solution is cooled and then treated with NaOH to liberate ammonia
gas:
NH/ + HO- -+ NH3(gJ + H10
• Glass or porcelain beads are added to avoid bumping
• In some modifications, hydrogen peroxide is added to decompose organic matrix
formed ·
'
• If mercuric oxide, HgO is used as a catalyst, it is necessary to add sodium
thiosulfate, Na 2S 2 0 3 to precipitate mercuric sulfide, HgS.
Hg 2+ + S203·2 + 2H0- 1 -+ HgScsJ + S04·2 + H10
Step 3. Titration
'"""""
NaOH solution
H,~
lJJ
1. Using an excess amount of HCl .. .
NH 3 + HCl
-+
NH4 Cl
The excess HCl is dete1mined using a standard NaOH solution
HCl + NaOH -+ NaCl + H20
2. Ammonia distilled is collected in a boric acid solution .. .
H3 + H3B03 !:+ NH/ + H1B03·2
Titrate the H3B0 3-NH3 solution with standard acid .. .
H1B03·2 + H30 + !:+ H3B03 + H 20
Percentage Protein in the Sample
% protein=% N * f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)
49
Analytical Chemistry
Physical and Chemical Principles
Double Indicator Method (Mixture of Bases)
• The presence of hydroxide, carbonate and bicarbonate in water is also referred to as
alkalinity which is a measure of the acid-neutralizing capacity of water
• One method requires titration of the mixture to reach the phenolphthalein endpoint
w_ith the volume recorded as Vo-Ph· On the same solution, methyl red is then added
and an additional vol um£_ is required to reach the end point recorded as VPh-MR
• Another method requires two duplicate samples. One sample is treated with
phenolphthalein and the other with methyl red. Volumes of titrant required to reach
the phenolphthalein and methyl red _endpoints are recorded as Vo-Ph and Vo-MR,
respectively
··
• m-Cresol purple can also be used to detect phenolphthalein alkalinity (P) while
bromocresol green or methyl orange for the total alkalinity (T)
Alkalinity relationships
Result from titration
V0-Ph > VPh-MR
V0-Ph < VPh-MR
V0-Ph = VPh-MR
Vo-Ph"" 0; VPh-MR> 0
V0-Ph > Q ; VPh-MR"" Q
Na OH
V0-Ph - VPh-MR
0
0
0
Vo-Ph
-
0
2VPh-MR
2Vo-Ph
2Vo-Ph = 2V Ph-MR
-
Ph
VPh-MR - V0-Ph
0
0
0
VPh-MR
0
Note: If analysis involves measurement of volume due to total alkalinity (Vo-MR), use the conversion: VPh-MR =
V0-MR - Vo-Ph
••••••••••••••••••••••••••••••••••••••r••••••••••••••1
''
''
'
:··--·-··-·:
i'
l Vo-Ph l
'
l
r····"··---~
~----T·--- 1
i Vrh-MR l
i
'
'
1
--_l::::r· r-~~=-1
_________ :~----.-~C~~:..,......i
~
(
0
Dete
Precipitation Titration
One of the oldest analytical techniques that started in the mid-1800's. Silver nitrate
(AgN0 3) is commonly employed in such technique. Titration with AgN0 3 is often
termed as argentometric titration .
: rm
Indicators in Precipitimetry
The equivalence point can be observed by the following:
~en
a.
Formation of a colored secondary precipitate
Mohr Method (K.F. Mohr, Germany, 1865)
Direct method for halides and cyanides
Titrant: Silver nitrate, AgN0 3
Titration Reaction: Ag++ Cr 1 -+ AgClcsl
White
Indicator: sodium chromate, Na2 Cr0 4
50
A
B
E1
Physical and Chemical Principles
Analytical Chemistry
Indicator Reaction: 2Ag+ + CrOl
-+
Ag2 Cr04(sl
red
Primary Standard for AgN0 3 : NaCl
Titration is carried out between pH of 7- 10. Usually, a low concentration of
chromate is desired to detect the end point clearly since a chromate ion imparts an
intense yellow color.
b.
Formation of a colored complexion
Vo/hard Method (Jacob Volhard, Germany, 1874)
Direct method for silver - Indirect method for haliq.es
Titrant: Potassium thiocyanate, KSCN
.
Direct Titration Reaction: Ag++ SCN"" 1 -+ AgSCNcsJ
white
Indirect Titration Reactions: Ag-+ + Cr'
-+
excess
AgClcsJ
white
Ag++ SCN"" 1 -+ AgSCNcsJ
white
Indicator: ferric alum
Indicator Reaction: Fe+3 + SCN·'
-+
Fe(SCN)2+
red
Titration is carried out in acidic condition to prevent precipitation of ferric ion to its
hydrated oxide form.
Formation of a colored adsorption complex ·
Fajans Method (K. Fajans, Poland, 1874)
Titrant: Silver nitrate, AgN0 3
Titration Reaction: Ag+ + er' -+ AgClcsJ
white
Indicator: dichlorofluorescein, best for determination of halides and cyanides
End point: color change from yellow to pink
Titration is carried out between pH of 4-7. Dextrin is added to prevent excessive
coagulation of the AgCl precipitate.
Complex Formation Titration
This type of titration is used for the determinations of cations. Typical reagents used
-~e organic compounds containing groups which are electron donors and have the ability
· form multiple covalent bonds with the metal ion.
Determination of Cyanide by the Liebig Method
The titration is carried by the dropwise addition of AgN0 3 in a solution of a cyanide
rrning a soluble cyanide complex of silver: 2CN"" 1 + Ag+ -+ Ag(CN) 2- 1• The endpoint
-=the titration is the formation of a permanent faint turbidity: Ag(CN) 2- 1 + Ag~ -+ Ag
--\g(CN)2]csJ
ermination of Nickel
An ammoniacal solution of nickel is treated with a measured exces& of standard
anide solution and the excess is determined by a standard AgN0 3 solution according to
-e reactions:
Addition of Excess Cyanide: Ni(NH 3) /3 + 4CN- 1 + 6H 20-+ Ni(CN) 4- 1 + 6NH40H
1
1
1 Back Titration with Ag+: 2CN- +Ag+ -+ Ag(CN) 21
Endpoint: Ag(CNF +Ag+ -+ Ag[Ag(CN)2]csJ
51
Analytical Chemistry
Physical and Chemical Principles
Titration with Ethylenediaminetetraacetic Acid (EDTA)
The structure suggests six potential sites (hexadentate) for metal bonding: the four
carboxyl groups and two amino groups. Commercially, the free acid and the dehydrate
are available. Solutions of EDT A combines with any metal ions in a 1: 1 ratio . The
indicator used for titration is the Eriochrome Black T®. For metal ion detections, it is
necessary to adjust the pH to 7 or above so that the blue form predominates in the
absence of a metal cation. Generally, metal complexes with EDT A are red as H2In- 1.
When an excess EDT A is added, the solution turns blue according to the reaction:
Mln- 1 + H\'3 :+ Hln-2 + MY-2
blue
red
Direct Titration with Added Metal Jons
In the determination of Ca2+, small amount of magnesium chloride is added to
EDTA. Initially, Ca+2 displaces Mg+2 in the EDTA complex and the latter combines with
EBT producing a red complex. When all the calcium is titrated, the liberated Mg+2 is
released, combined with the EDT A and the endpoint is observed.
Introduction to Electrochemistry
An oxidation/reduction reaction is one m which electrons are transferred from one
reactant to another. Oxidation reaction involves an increase in the oxidation state of an
element while reduction reaction involves a decrease in the oxidation state. Consider the
reaction:
In this reaction, Ce4 + ion
acquires an electron from
Fe 2+. Such strong electron
affinity for electrons makes
Ce4 + an oxidizing agent or an
oxidant. On the other hand,
Fe 2+ readily gives its electron
and is a reducing agent or
reductant.
For oxidation reaction .. .LEORA
!;oss of Electron(s), Q xidation, substance oxidized is
the Reducing Agent
For reduction reaction .. .GEROA
Qain of Electron(s), Reduction, substance reduced is
the Q xidizing Agent
Balancing Redox Reactions
Step 1. Assign oxidation numbers of each of the species in the reaction
Mn0 4- 1 + 0 2- 1 -+ Mn 2- -L 0 3- 1 (acidic medium)
+7 -2
+3 - 2
+2
-5
-~
Step 2. Write the half-cell reactions. Identify oxidation ·and reduction reactions. If
compounds are present in the reaction. u e the ions in the half-cell reaction
OXIDATIO : N02- 1 -+ N03- 1 + 2e-3
REDUCTION:
+5
Mn0 4- 1 +Se- -+ Mn-~
- :?
+7
Step 3. Balance the reaction by multiplying a fac tor so that the number of electrons on
both sides is the same.
5 0 2- 1 -+ ~ . ro 3- 1 + lOeOXIDATIO x 5:
+3
REDUCTION x 2:
-5
2Mno~- 1
-
l Oe-+ 2Mn+2
+2
I
52
Analytical Chemistry
ysical and Chemical Principles
.::-ep 4. Balance by adding H2 0 to the oxygen deficient side and H+IOH- on the other
side.
5N0 2- 1 + 5H2 0 -+ 5N0 3- 1 + IOW + lOeOXIDATIO x 5:
-3
+5
2Mn0 4- 1 + I6W + IOe- -+ 2Mn+2 + 8H20
REDUCTION x 2:
+2
+7
E ectrochemical Cells
Electrochemical cells have two electrodes, which are immersed in an electrolyte
ution. Salt bridges are used to prevent the two solutions from mixing.
The cathode in an electrochemical cell is the electrode where reduction· occurs. The
_ _ e, on the other hand, is where oxidation occurs . .
A galvanic or voltaic cell is an electrochemical cell that stores electrical energy. The
__ tiori. at the anode and the cathode occurs spontaneously and allows flow of electrons
m the anode to the cathode with the aid of an external conductor.
In contrast, an electrolytic cell requires an external source of electrical energy to
te.
zematic Representation of Cells
Cu I Cu2+ (0.0200M) II Ag+ (0.0200M) I Ag
A OD!C REACTTO
CATH OD IC REACTTO
:: ectrode Potentials
An electrode potential is the potential of a cell with the hydrogen electrode as the
e. Standard Hydrogen . Electrode (SHE) is assigned a value of O.OOOV at all
peratures. The standard electrode potential, E 0 of a half reaction is the electrode
- ential when the activities of all reactants and products are unity (1 M molar
entration and 1 atm partial pressure).
1dard Reduction Potential
A positive value of the standard reduction potential of an electrode implies that it
- used as cathode with the SHE as anode. High positive value of a reduction potential
- indicates that the electrode is a good oxidizing agent.
ennodynamic Potential of an Electrochemical Cell, Ecell
This potential can be computed at standard conditions as follows:
Ecell = Ecathode - Eanode
::- ect of Concentration on Electrode Potentials: Nernst Equation
At 25°C:
E=E
0
E= E
0
-
-
RT Jn [C]c[Df ··
nF
[A] 8 [B]b ...
0.0 592 loo [C]c[p]d···
n
where:
Nemst Equation
"'
[A] a [BJ b ...
R =gas constant, 8.314 1K -mol
T = temperature in Kelvin
n = number of elyctrons that appear in the half-cell reaction
F =Faraday' s constant, 96487.38 coul/
_
/ molee
53
Physical and Chemical Principles
Analytical Chemistry
Oxidation-Reduction Titration
a.
Permanganate Process (KMnO.J
In acidic medium ... Mn0 4- 1 + 8H+ + 5e- - Mn 2+ + 4H 20
. In basic/neutral medium ... Mno4- 1 + 2H 20 + 3e- - Mn02 + 4HOStandardization of KMn04 solution
Indicator: self indicating
Primary Standards
I. Against Na 2C204
Rxn: Cz0 4-2 - 2C02 + 2e2. Against As 20 3
Rxn: As 3+ + 4H 20 - H 3As04 + 5H+ + 2e3. Against Ferrous solutions
Rxn : Fe 2+ - Fe3+ + e4. Against pure Fe
Rxn: Fe - Fe 2+ + 2eApplications ofPermanganimetric Titrations
1. Fe2+ - Fe3+ + e2. Sn 2+ - Sn 4+ + 2e3. N0 2- - N0 3- + 2e4. H20 2 - 0 2 + 2e5. Mo 3+ - Moo/- + 3e6. Ti 3+ - Ti0 2+ + e-
b.
Dichromate Process
Rxn: Cr2o t + 6e- - 2Cr3+
Indicator: sodium diphenylbenzidine sulfonate
barium diphenylamine sulfonate
Applications of Dichromate Process
1. Fe2+ - Fe3+ + e2. U4+ - uo/+ + 2e3. Cu+ - Cu+2 + e-
c.
Iodometric Titration (Indirect Titration with Iodine)
Rxn: I2 + 2e- - 2rTitrant: a2S20 3
Indicator: starch
Primary Standard: K2Cr20 7 (Cr20 7- 2 + 6r- - , 2Cr3+ + 31 2)
Titration Reaction: 2S 20 3- 2 + Ii - S40 6-2 + 2I-
The Absorption of Radi~tion: Ultraviolet and Visible
If a beam of light passes through a glass container filled with liquid, the emergen:
radiation is always less powerful than that entering. If the energy absorbed is greater fosome visible wavelengths than for others, the emergent beam will appear colored.
I
54
Physical and Chemical Principles
Analytical Chemistry
Beer's Law
The absorption of radiant energy by matter can be described using Beer' s Law.
,... onsider a block of an absorbing material of concentration, c and thickness, b:
,...
b
...,
,____ _ ., p ..
:>
• 0
·I
II
-+I I+-
I
p
A= loo-_£_= Ebe
"'p
1
A=loa-=£bc
dx
"'r
here: T = transmittance; A = absorbance; P
-orptivity; P 0 =entering radiation
emergent radiation; c
molar
REVIEW QUESTIONS AND PROBLEMS
All of the following is used as a hygroscopic material in desiccators except
a. CaS04
b. Mg(Cl0 4) 2
c. P20 5
d. CuS0 4
- Analytical methods classified as micro analyses use sample mass ranging from
a. < 1 mg
b. 1-10 mg
c. 10-100 mg
d. > 100 mg
_. Chemicals which are tested by the manufacturers showing the actual percentages of
impurities and labeled on the containers are called _ _ _ __
a. reagent grade chemicals
c. certified reagent
b. analytical reagent
d. all of these
-
What proportion by weight ofNa 2C20 4 (134) to that ofK.HC2 0 4 ·H2 C2 0 4 (218.2) that
must be mixed in a solution so that the normality of the resulting solution as a
reducing agent is three times the normality as an acid?
a. 3.07
b. 1.54
c. 0.65
d. 0.33
Platinum crucibles can be used for the following processes without significant loss
except
a. Fusion with sodium carbonate, borax or alkali bifluorides
b. Evaporation with hydrofluoric acid
c. Ignition of oxides of Ca and Sr
d. Heating with sulfides
~
What volume of water must be added to concentrated HCl solution to prepare 100
mL 0.955 M HCI solution?
a. 7.9 mL
b. 15 .8 mL
c. 46.0 mL
d. 92.1 rnL
- What grade of water as defined by the British Standard 3r is suitable for the
determination of trace quantities which can be prepared by the distillation of deionized water?
a. Grade 1
b. Grade 2
c. Grade 3
d. Grade 4
55
Physical and Chemical Principles
Analytical Chemistry
For numbers 8 to JO ...
A 20% wt/wt aqueous solution of NaCl (58.45) at 25°C has a density of
1.145 g-mL- 1• Express the amount of solute in this solution as follows:
8. % wt/vol
a. 17
b.19
c.21
d.23
9. molarity (M)
b. 1.96
c. 3.92
d. 5.88
a. 0.98
IO. molality (m)
a. 4.28
c. 6.84
b. 5.13
d. 8.56
11. The following describes colloidal suspensions formed during precipitation except
a. These particles are almost invisible to the naked eye
b. They settle readily from a given solution
c. They are not easily filtered
d. none of the these
12. A 1.5176 g sample of a CaC0 3 was dissolved in an acidic solution. The calcium was
precipitated as CaC2 0 4 ·H20 (146.11) and the ignited precipitate at 230°C was found
to weigh 0.8249 g. What is the percentage ofCaO (56.08) in the sample?
a. 20.9%
b. 23.8%
c. 41.8%
d. 47.6%
13. A mixture containing FeC13 (162.20) and AlCh (133.33) only weighs 750.8 mg. The
chlorides were precipitated using ammonia and ignited to Fe2 0 3 (159.69) and Ali0 3
(101.96), respectively. The oxide mixture weighs 351.3 mg. Calculate the percentage
of Al (26.98) in the sample.
a. 1.5%
b. 4.5%
c. 7.5%
d. 10.5%
14. Which of the following does not describe the correct way to wash precipitates?
a. Minimum volume of washing liquid must be used to wash the precipitate
b. Wash with small portions of washing liquid
c. Ionic salts containing common ion must be added to the washing liquid to
increase the solubility of the precipitate
·
d. Gelatinous precipitates require more washing than crystalline precipi"tates
15. What is the extent of ionization of the second proton of0.5 M H2S04 at 25°C?
a. 1%
b. 2%
. c. 4%
d. 8%
16. It is the expressed as the volume of a solution chemically equivalent to a mass of a
solid reagent
a. titer
b. aliquot
c. molarity
d. ppm
17. What weight of Mn ore should be taken so that the percentage of Mn0 2 (86.94) -in
the ore would be twice the mass of Mn 30 4 (228.82) precipitate obtained in
milligram?
b. 38 .0 mg
c. 57.0 mg
d. 76.0 mg
a. 19.0 mg
18. Process by which an agglomerated colloid return to its dispersed state during
washing due to leaching of electrolyte responsible for its coagulation
a. nucleation
b. coagulation
c. agglomeration
d. peptization
19. Which of the following aqueous solutions of the same concentration will have the
largest pH value at 25°C?
a. NH 3
b. KC!
c. NH 4 Cl
d. NaF
56
Physical and Chemical Principles
Analytical Chemistry
20. Which of the following solutions at 25°C will have the lowest pH value?
a. 0.15 M Na2 S04 (KA2 ofH 2 S04 = 1.2 x 10-2)
b. 5.2 x 10- 8 M HCl
c. 0.05 M NaCN (KA ofHCN = 6.2 x 10- 10)
d. 0.01 M NH 4Cl (KA ofNH/ = 5.6 x 10- 10)
21 . Which of the following acid-oase pairs will result in the formation of a buffer
solution when titration is done before the equivalence point?
a. NaOH and HCl
c. NH 3 - HBr
b. KOH - HN0 3
d. all of these
_2. What volume of 0.1025 M HCl must be added to 15.64 mL of 0.0956 M NH 3 to
produce a solution of pH= 9.00?
a. 5.3 mL
b. 7.3 mL
c. 9.3 mL
d. 11.3 mL
_3. Which of the following statements is not correct?
a. The buffer capacity is always a positive number
b. The larger the buffer capacity, the more resistant the solution is to pH change
c. In general, alkaline buffering capacity is maximum over a pH range of p:K.i,± 1
d. The acid buffering capacity is maximum at pH equal to pK.
_4. Approximately how many grams of NH4Cl (53.45) should be dissolved in a liter of
0.125 F NH 3 to reduce the concentration of hydroxide ions to one-thousandth of its
original value?
a. 79.1 g
b. 62.5 g
c. 11.7 g
d. 7.91 g
The conjugate base of H 2P0 4-l is _ _ _ __
2
a. HP0 4b. P04-3
c. H3P04
,:6. In the standardization of an acid solution with primary standard sodium carbonate,
why is it necessary to boil the solution before completing the titration?
a. to eliminate the reaction product, carbon dioxide and carbonic acid
b. to destroy the buffering action of the resulting solution due to the presence of
carbonic acid and unreacted hydrogen carbonate
c. to achieve a sharper endpoint with methyl red indicator due to the large
decrease in pH
d. all of the these ·
Calculate the molarity of NaOH solution if 12.25 mL was used to titrate 0.2615 gram
of primary standard KHP .
a. 0.1045
b. 0.1354
c. 0.2509
d. 0.1697
What is the best basis for choosing the right indicator for a given acid - base titration
from among the following?
a. type of acid
c. pH at equivalence point
b. type of base
· d. melarity of the acid or base
-~·
In standardizing a solution of NaOH against 1.431 grams of KHP, the analyst uses
35.50 mL of the alkali and has to run back with 8.25 mL of acid (l mL = 10.75 mg
aOH) . ·What is the molarity of the NaOH solution?
a. OQ l 18 M
b. 0.2044 M
c. 0. 7831 M
d. 0. - 598 M
In the titration of a weak acid with a strong base, which of the following is the best
indicator to be used?
a. bromocresol green
b. methyl orange
c. methyl red
d. phenolphthalein
57
Physical and Chemical Principles
Analytical Chemistry
31. A 0.2055-g sample of calcite (impure CaC0 3) is treated with 27.18 ml of0.0712
HCl and the excess is found to require 5.44 ml of 0.0869 N NaOH for back titration.
Calculate the percentage purity of calcite in terms of% wt/wt CaC03 ( 100).
a.17.8%
b.35.6%
c.53.4%
d. 71.2%
32. · Process of determining the nitrogen content of organic materials by mixing the
sample with powdered copper (II) oxide and ignited to a combustion tube giving
C0 2, H 20 , 2 and small amounts of nitrogen oxides.
a. Kjeldahl Method
c. Winkler Method
b. Dumas Method
.. d. Wij's Method
For numbers 33 to 35 ...
A 500-mg sample of each mixture was analyzed for its alkaline content using 0.102:
M HCl via double indicator method.
4
3
Mixture
1
2
5
6.37
5.12
Vo-Ph(mL)
4.27
0.01
5.63
10.24
6.38
9.04
10.18
6.19
Vo-MR (mL)
33. Which of the following mixtures contains NaHC0 3?
a. Mixtures 2 and 4
c. Mixtures 3 and 4
b. Mixtures 4 and 5
d. Mixtures 1 and 2
34. Calculate the purity of the sample containing NaHC0 3 only.
a. 1.82%
b. 5.22%
c. 10.64%
d. 11.13%
35 . What is the% wt NaOH for the sample containing a mixture ofNaOH-Na2C0 3?
a. 1.82%
b. 5.22%
c. 10.64%
d. 11.13%
36. In the analysis of nitrogen using Kjeldahl Method, which of the following is added t
decompose organic matrices present in the sample?
a. H2S04
b. HgO
c. K2S04
d. H 20 2
37. A 7.279-gram sample of meat was analyzed for its nitrogen content using Kjeldat..
Method. Upon digestion, the ammonia liberated was collected in 250 mL of 0.855 ..
H 3B0 3. The resulting solution was titrated with 37.25 mL of 0.3122 M HCl us in~
mixed indicator. Determine the % protein in the sample using 6.25 as factor for me
products.
a. 13 .98%
b. 2.24%
c. 19.69%
d. 3.14%
38. \\ill h of the following is not used as primary standard for the standardization
alkali solutions?
a. HgO
39. A 1.500-gram sample
treated with 45 ." _ mL
analysis in %AlCl3 l"
a. 40.28%
of impure afumim1m chloride was dissolved in water an:
of 0.1000 M AgN0 3 using K2Cr0 4 as indicator. Express L
.33).
b. 13.43%
c. 4.48%
d. 27.36%
40. Which of the following i not a correct analytical method-titrant Vair?
a. Mohr-AgN03
c. Volhard-AgN0 3
b. Fajans - AgN0 3
d. Liebig - AgN0 3
'
41. A mixture of LiBr (86.845) and BaBr2 (297.22) weighing 800 'T~ _is treated wi-·
50.00 mL of 0.1879 M AgN.0 3 and the excess is found to require ~~ mL of 0.3 1- ·
M KSC for back titration, using ferric alum as indicator. What is the percentage
BaBr2 in the sample?
a. 67.95%
b. 32.05%
c. 35 .62%
d. 64.38%
58
Physical and Chemical Principles·
Analytical Chemistry
42. A 500-mg sample containing NaCN required 23.50 mL of 0.1255 M AgN0 3 to
obtain a permanent faint turbidity. Express the result of this analysis as% CN-.
a. 15.34%
b. 23.01 %
c. 17.25%
d. 30.67%
43. In Volhard Method, why is it necessary to carry out titration in acidic solution?
a. To prevent precipitation of iron as hydrated oxide
b. To prevent formation of AgSCN precipitate
c. To prevent reduction of halide
d. To prevent precipitation of silver as hydrated as hydrated oxide
44. A 750.25-milligram alloy of nickel was dissolved and treated to remove the
impurities. Its ammoniacal solution was treated with 50 mL of 0. 1075 M KCN and
the excess cyanide required 2.25 mL of 0.00925 M AgN0 3. Determine %'Ni (58.69)
in the alloy.
a. 20.86%
b. 37.69%
c. 10.53%
. d. 41.72%
45. Which of the following ions is best titrated with EDTA at minimum pH less than 7?
b. Sr+2
c. Mg+2 .
d. Fe+3
a. Ca+2
46. An EDT A solution was prepared by dissolving the disodium salt in 1L of water. It
was standardized using 0.5063 gram of primary standard CaC03 and consumed
28.50 mL of the solution. The standard solution was used to determine the hardness
of a 2L sample of mineral water, which required 35 .57 mL of the EDTA solution.
Express the analysis in terms 0fppm CaC0 3 .
a. 89 ppm
b. 316 ppm
c. 158 ppm
d. 269 ppm
47. Which of the following statements is true?
a. Multidentate chelating agents form weaker complexes with metal ions
b. All metals can be determined with high precision and accuracy using
chelometric titration
c. Eriochrome black T gives a sharp endpoint for the titration of calcium
d. Ca-EDT A complex is more stable than Mg-EDT A complex
48. The 300 mg sample of impure Na2 S0 4 (142.04) was dissolved in sufficient water and
the sulfate was precipitated by the addition of 35.00 mL of 0.1022 M BaC!i. The
precipitate was removed by filtration and the remaining BaC!i consumed 6.79 mL of
0.2467 M EDT A for titration to the Calrnagite endpoint. Calculate the purity of the
sample.
a. 80%
b. 85%
c. 90%
d. 95%
a
.+9. Commonly, the analyte in sample is present in two different oxidation states. Prereduction is then necessary before titration. One of the metallic reductors is zinc
soaked in a dilute solution of mercuric chloride. This reductor is known as
c. Lindlars catalyst
d. Jones redactor
a. Walden reductor
b. Devarda Alloy
-o.
At pH = 7 and a pressure f 1 bar, the potential for the half reaction, 2H+(aq) + 2eis
a. 0 V
H 2(g)
"" A
b. - "{14 V
c. -0.828 V
d. -1.255 V
-1. Which of the following is false about iodine as an oxidizing agent in titration?
a. Standard iodine solutions have low smaller electrode potential
b. Sensitive and reversible indicators are readily available
c. Iodine is very soluble in water and losses are minimal
d. The solution lacks stability and requires regular standardization
59
-+
Physical and Chemical Principles
Analytical Chemistry
52. All of the following is used as oxidant in redox titrations except
a. KMn0 4
.b. Cerium (IV)
c. K2Cr20 7
d. Kl
53. What is the molarity of a KMn0 4 solution standardized against 1.356 gram Na2C20 4
(134 glmol) requiring 25.l mL of the solution in acidic medium?
a. 0.161 M
b. 0.403 M
c. 1.008 M
d. 0.856 M
54. A sample of iron ore weighing 385.6 mg was dissolved in acid and passed through a
Jones reductor. The resulting solution 52.36 mL of0.01436 M K2Cr20 7 for titration
to the diphenylamine sulfonic acid endpoint. Calculate % Fe30 4 (231.55 glmol) in the
"
ore sample.
a. 15.05%
b. 45.15%
c. 90.30%
d. 67.98%
55. A sample ofpyrolusite weighing 0.2400 gram was treated with excess Kl. The iodine
liberated required 46.24 mL of 0.1105 M Na2 S20 3 solution. Calculate % Mn0 2
(86.94) in the sample.
a. 46.27%
b. 30.85%
c. 92.54%
d. 76.12%
56. Which of the following metal is not reduced by Walden reductor?
a. Cr
b. Fe
c. Cu
d. V
57. A 10.00 gram sample of cooked-ham was pureed with 200 mL of water, filtered and
the resulting solution containing dissolved potassium nitrite was acidified. This
solution was treated with 25.00 mL of0.00514 M KMn0 4 and was back titrated with
14.97 mL of0.01678 M FeS0 4 . Calculate the amount of nitrite (46.01) in ppm.
a. 450
b. 900
c. 1350
· d. 1800
58. Which of the following is used as a pre-oxidant?
a. sodium bismuthate
c. sodium peroxide
b. ammonium peroxydisulfate
d. all of these
59. A 100 mL water sample was analyzed by Winkler Method. If7.52 mL of0.0124 M
a2S20 3 was used for titration, determine the ppm of 0 2 in the water sample.
a. 2.8
b. 3.5
c. 6.4
d. 7.5
60. A 500 mg sample of a solution containing cobalt (58.93) and nickel (58.69) was
dissolved and diluted to 500 mL. A 25 mL aliquot was treated with a complexing
agent to produce a colored complex and the volume was adjusted to 50 rnL. The
following data were obtained for the simultaneous determination in a 1.00-cm cell:
Wavelength
(nm)
510
656
Molar absorptivity, £ [M- 1-cm- 1]
Co
Ni
36400
5520
1240
17500
Calculate the concentration of Co in the solution in ppm
a. 1172 ppm
b. 1940 ppm
c. 2142 ppm
60
Absorbance of
solution, A
0.815
0.314
d. 2343 ppm
Physical and Chemical Principles
Physical Chemistry
D. PHYSICAL CHEMISTRY
Physical Chemistry
Branch of chemistry that deals with the study of the structures and physical properties of
matter with the laws of chemical interaction and the theories governing these interactions
Types of Microscopic or Mechanistic Descriptions
1. Newtonian Mechanics and Electrostatics
Involve the kinetic theory of gases and its application to solutions and Debye-Huckel
theory of electrolytes
2.
Viewpoints and'Considerations
Microscopic. Involves motion of individual molecules and individual electronic,
spin, vibrational and rotational energy transitions
Macroscopic. Involves measurement of properties of matter as a bulk such as
pressure, temperature, volume, absorbance, etc.
Properties of Matter
Properties
Density
Solid
high
Compressibility
incompressible
Volume and Shape
shape and volume
is definite
Molecular Motion
vibrate on fixed
Eositions
States of Matter
Liguid
high
slightly
compressible
volume is definite
but takes the shape
of the container
slide past one
another
Gas
low
very compressible
assumes the shape
and volume of the
container
free motion
Other States of Matter
1. Plasma - results from a mixture of neutral atoms, free electrons and charged ions,
usually a fluid but due to charged particles present, it responds to and generates
electromagnetic forces
Bose-Einstein Condensate - special state of matter in which atoms in a confined
gas act together like a single giant particle after being cooled cryogenically to a
temperature near absolute zero
Ideal Gases
..\. State of a System
• refers to the physical state of a gas specified in terms of its physical properties
like its volume (V), pressure (P) , temperature (T) and number of moles (n)
• experimentally, it is sufficient to specify three properties to fix the state of a
system
B. Kinetic Molecular Theory
1. Gases are considered to be composed of minute discrete particles called molecules.
2. The molecules within a container are believed to be in ceaseless chaoti motion
during which they collide with each other and with the walls of the onrainer.
3. Inasmuch as the pressure of a gas within a container does not rnry with time at
any given pressure and temperature, the molecular collisions must involve no
energy loss due to friction . In other words, all molecular olli ions are perfectly
elastic.
4. The absolute temperature is a quantity proportional to the average kinetic energy
of all molecules in a system.
61
Physical and Chemical Principles
Physical Chemistry
5. At relatively low pressures, the average distances between molecules are large
compared with molecular diameters, and hence the attractive fo rces between
molecules may be considered negligible.
6. Since the molecules are small compared with distances between them, their
volume may be considered to be negligible compared with the total volume of the
gas.
C. Distribution of Molecular Speeds
1. Maxwell-Boltzmann probability distribution
l
g(v)= _ m
__
2Trk 8 T
(
2
J
mv 2
e- 2k/JT
where: k8 =Boltzmann constant, 1.380 6503 x 10- 23 J-K- 1
2. Speed probability distribution or probability density
~
ffi \'2
fv(v) = 411v2 (~J2 e 2ksT
2rck 8 T
3. Most probable speed
_ dfvl
_
dv v=O
Vp -
I
~2k 8 T -_ ~ 2RT
m
M
4. Mean speed
(v) =
io~
T ~8RT
vfv(vJlv = ~k
- 8 -=
mn
nM
5. Root-mean-square speed ·
vnn, = (v2)~ =
I
.
[r v2 rv(v}lv J2 = pk;T = p~T
D. Derivation of Ideal Gas Equation of State
Consider the basic ewtonian mechanics of small particle
of mass, m and velocities, vx, vy and V: along the Cartesian
coordinates in a. cubical container of side, L .. .
If a single molecule of velocity, Vx and mass, m from the
other end of the cubical container collides with plane yz,
it will rebound at a velocity of (- vx) to the opposite
direction since the collision is perfectly elastic. The
change in momentum (!¥1.J per molecule in the xdirection is
f¥l x = mvx - m(- vJ = 2mvx
The total time travelled by the molecule to hit the other
end and back to its original position is
2L
t =-
vx
Therefo re the change in momentum per unit time for the
molecule in the x -direction is
t:,.p-, _ 2 mv ( -v, ) - mv;
-t
T
2L
L
62
·---
m
Ux
.......
Physical and Chemical Principles
Physical Chemistry
The total force, F exerted on the wall for N molecules of the gas is
F
= Nflp x = Nm (v 2 )
t
L x
With the assumption of molecular chaos (assumption that the velocities of colliding
partides are uncorrelated and independent of position) ... then the pressure exerted on
the area of the wall. . .
2
P = £_ = Nm( v
A
· 3L
2
1- ) = Nm( v )_and since V = L3 and (v 2 ) = 3RT then
"
3L3
M
L2
) (-
2
P = Nm(v ) = Nm ( RT ) = nRT
3L3
M
V
V
where N = number of molecules, m = mass of each molecule (g-molecule- 1) and M =
molar mass (g-mor 1)
E. Ideal Gas Equations
I :~ = R I
+n
m
~
m
Values ofR
1
8.314 - mol - K
1.987~ ·
1 mol
=
mol - K
n = m l M,+
0.08205 L - atm
mol - K
~
~
p =m/V
10.73 ft 3 -psia
lbmol - R
+
~
ISOBARIC
LEJ
I
~ ~
=
ISOTHERl\1AL.
=k I
I PY = RT=k
CHARLES' LAW
BOYLE'S LAW
ISOCHORIC
11
~ ~
=
=k I
GAY-LUSSAC'S LAW
+'-----~---'•--...--------'·
•
V = RT = k
p
AMA GA T'S LAW OF
PARTIAL VOLUME
'··································
DALTON'S LAW OF
PARTIAL PRESSURE
,-----------.--------- -
- - - - - - - - - - - - - - - -,_ M_l~!¥J3~ Qf !~~~1:_ <:!~~E_S_ _; - - -
63
. i=I
J
~ ................................~
-- - -- - - - - - -- "
Physical and Chemical Principles
Physical Chemistry
y
F. Molecular Weight Determination
1. Method of limiting density
a. involves measurement of density of a
gas at various pressures at constant
/
0
temperature
p(
g )
0
b. a plot of p/P against P is obtained
p L- atm
wherein the -intercept corresponds to
•0
(p/P)p~
.....
c. at zero pressure, ideal gas law becomes ( P )
• ........ •••••
exact for all gases
P P=0
~------- x
2. Vapor density method
Developed by Jean Baptiste Andre Dumas to determine molecular weight in the
vapor phase of volatile liquids
a. A retort-shaped bulb, having a small opening to capillary tube is filled with
air and weighed
b. The sample of liquid is drawn into the bulb by cooling it and then immersed in
a bath with temperature above the boiling point of the liquid
c. Boiling allows removal of excess air and complete vaporization of the liquid
d. The flask is then sealed, cooled to room temperature and weighed
3. Regnault method
Developed by Henri Victor Regnault used to determine molecular weight of gases
at room temperature
a. A dry gas bulb of300-500 mL capacity is evacuated and weighed
b. At a definite temperature and pressure, the bulb is fi lled with gas and weighed
c. The bulb is then fi lled with a liquid of known density and weighed
•
Real Gases
A. Equations of State for Real Gases
1. van der Waals equation of state
Johannes Diderik van der waals (1837-1923) received Nobel Prize in 1910
[
P + - a?
V ;;,
l( )
Vm - b = RT
.
2T~
2
27R
and b = V me = RTe
where a =3Vme
pe = --~
64Pe
3
8Pe
2. Virial equation of state
PVm - 1 B 2 B3
B4
-- - ++ - 2 + - 3 + ...
RT
vm VITI vm
3. Berthelot equation of state
[
P+--;-J(vm - b) = RT
TVm
T:
2
2
where
a=
9RTCVmc 27R
- - - 8
64Pc
vme RTe
and b = - - = - 3
8Pe
4. Dieterici equation of state
a
P =~ e- VmRT
Vm- b
2
2
4R T
V
where a = 2RTeV me = - -e_ and b = _!!!£_
Pe
e
2
2
64
RT
= __
e
2
Pe e
I
Physical Chemistry
Physical and Chemical Principles
5. Redlich-Kwong equation of state
P =~
a
T!vm(Vm +b)
Vm - b
B. Compression Factor and Boyle Temperature
1. Compression factor, Z
• Ratio of the measured molar volume, Vmto the molar volume of an ideal gas,
VJG at the same pressure and temperature
· ;· ;
]
f
]
.
JG
RT
. Vm
Vm
:
: )
:
"'
• Smee Vm = - , then Z = ---io = "RT
p
vm p
i
u .
~
PV
and Z= -
-m
RT
Measure of departure from the ideal gas
behavior
For an ideal gas, Z=l
At low temperatures, Z<l for moderate
Pressure, P
pressures and Z> 1 as pressure increases
At high temperatures, Z> 1 for all pressures
Attraction between molecules results to reduction in the value of Z while
repulsion between molecules results to increase in the value of Z
Therefore, attractive forces are significant at low temperature and pressure
while repulsive forces are significant at high temperature and pressure
•
•
•
•
•
•
2. Boyle temperature
• The temperature at which the property of a real gas coincides with that of an
ideal gas as P ~ 0
• Although, the equation of state of a real gas may coincide that of an ideal gas
as P ~ 0 , not all its properties necessarily coincide with those of an ideal gas
in the given limit
• Mathematically, the Boyle temperature is the temperature at which Z ~ 1 and
dZ = O at low pressure and high molar volume . VM ~ 00
dP
Liquids
From the kinetic theory viewpoint, a liquid may be considered as a continuation of
the gas phase into a region of small volumes and very high molecular attractions.
A. Critical Phenomena in Liquids
•
•
•
•
•
When liquid is sealed in an evacuated tube, a certain amount will evaporate to
form vapor
As soon as equilibrium is established between the liquid and vapor, the pressure
exerted by the vapor is known as the saturated vapor pressure
When the critical point is reached, there will be no distinction between the liquid
and the vapor
At this point, the physical properties of liquid and vapor become identical
At this point, in general , no liquid can exist as such at temperatures above the
critical under any applied pressure
65
Physical and Chemical Principles
Physical Cner!2_;.
B. Viscosity
• Defined as the resistance offered by a fluid to the flow of another fluid
• Produced by the shearing effect of moving one layer of the fluid past another
• For gases, viscosity increases with increasing temperature
• At low pressures, viscosity is not affected by pressure
1. Viscosity of ideal gases
I
3
1]=- vlp
2.
where v = is the average velocity of t~.e gas molecules, 1 = is the mean free path
and p =is the density of the gas
Viscosity of liquids
a. Pouiseuille 's Equation (Ostwald Viscosimeter)
nPr 4 t
µ = 8LV
whereµ = viscosity [g-cm- 1-s- 1] , P=pressure head [dynes-cm-2], r=radius of
a capillary tube [cm], L= length of the capillary tube [cm], V=volume of the
fluid [cm3] and t=time of flow [s]
Using the Poiseuille equation; !he ratio of the viscosities using water as
reference liquid
µ water
(Pt )water {pt )water
µliquid = (Pt )iiquid = (pt )liquid
b.
Stokes ' Law (Falling Sphere Viscometer)
• This law is applicable when the radius of the falling body is greater than
the distance between the molecules of the fluid
• Stokes' law is given by tlte equation:
µ=
•
2r 2(P-Pm )g
9v
where r =radius of steel [cm], p, Pm= steel ball and fluid densities [gcm-3], g = 980 [cm-s-2] and v=terminaL velocity [cm-s- 1]
'
Using a reference liquid,
.&_ _ (P-Pm 1 )t1
µ2
(P - Pm)t2
C. Surface Tension
Amount of work required to increas.e the surface area of a liquid by one unit of
area.
This property can be measured in two ways:
1. Capillary-rise method
• When a capillary tube of radius, r is placed in a liquid of density, p that
wets its surface, the liquid is observed to rise at a height, h.
• Then the surface tension can be computed as
phgr
y=- -
2
2. du Nouy Ring Method
•
•
Device used in this method is known as tensiometer, which was
developed in Rockefeller Institute for Medical Research
The fundamental equation used is
66
Physical Chemistry
Physical and Chemical Principles
amg
y = 2L
where: m = weights necessary for the restoration of the tensiometer's
horizontal position and L=mean circumference of the ring and a =correction
factor
Solids
These have definite shape and volume, rigid and exhibit certain hardness.
Terminologies
1. Crystalline
• copstituent structural units are arranged in a definite geometrical configuration
characteristic ·of the substance
• melts sharply at a constant and definite temperature
Amorphous
• does not show a definite configurational arrangement
• not considered as true solids but highly supercooled liquids with very high
viscosity
• melts gradually over a temperature interval
j,
~.
Heat of Crystallization
• amount of heat evolved during crystallization or solidification per mole of
substance at a given temperature and pressure
Heat o\Fusion
• the r evers.e of heat ~~ crystallization which. is the amount of heat that must be
absorbed m the trans1t10n of one mole of solid to IIqmd
·
Crystallography
• a study dealing with the geometry, properties and structure of crystals and
crystalline substances.
6. Crystal Systems
• 230 possible crystal forms
• may be grouped into 32 classes according to symmetry
Six Crystal Systems
SYSTEM
Cubic
Tetragonal
Hexagonal
Orthorhombic
(Rhombic)
AXIAL CHARACTERISTICS
Three axes at right angles a = b
=c
Three axes at right angles with
two equal le.ngths
a = b;t:c
Two axes of equal lengths in
one plane making an angle of
120° with each other
A third axis at right angles to
these and of unequal lengths a
= b;t: c
Three axes at right angles, but
all of different lengths a ;t: b ;t:
c
67
MAXIMUM
SYMMETRY
EXAMPLES
Nine planes
Thirteen axes
NaCl, KC!, Alum,
Diamond, CaF 2
Five.planes
Five axes
Seven planes
Seven axes
Pbl2, Mg , Beryl,
CdS , ZnO
Three planes
Three axes
KN0 3, Rhombic
sulfur, K1S0 4,
BaS04 , PbC0 3
Physical Chemistry
ix Crystal Systems (continuation)
SYSTEM
AXIAL CHARACTERISTICS
MAXIMUM
SYMMETRY
EXAMPLES
Monoclinic
Three axes at right angles, but
all of different lengths a b 7cc
One plane
One axis
Na2S04 · lOH20,
CaS04 · 2H20,
Monoclinic sulfur
Triclinic
Three- axes at right angles, but
all of different lengths a* b 7cc
No planes
No axes
CuS04 · 5H20,
K2Cr01, H3B03
*
Polymorphism
•
•
existence of substances in more than one modification
examples include carbon exists as diamond or graphite, calcium carbonate as calcite
or aragonite
•
Allotropy
0
0
polymorphism occurring in elements
transformation from one form to another takes place at a temperature known as
transition temperature or transition point
Chemical Equilibrium
• state at which the net rate of all chemical reactions is zero
Gibbs-Helmholtz Equation
[
Relation of Kp and .6G
o(G!T)]
oT
.6G
t.H
p
T2
= -RTln(Kp)
Temperature ~ence of KP ·
Relationship of Kr and Kc
.6n g = n gas, product - n gas, reactant
Colligative Properties of Solutions
Properties that depend on the number of solute particles and the nature of the solvent
l. Lowering of Vapor Pressure:
0
.6P = P x solute
where: P 0 = vapor pressure of pure solvent, Xsolute = mole fraction of the solute in
the solution and .6P =extent of vapor pressure lowering
2. Elevation of Boiling Point
.6Tb = Kbm
where: t.Tb = Tb,solution - Tb,solvent>
Kb = ebullioscopic constant and m = molality'
,. 3. Depression of Freezing Point
.6Tr = K r m
where: .6Tr= T r,solvent - T f,soJn,
Kr = cryoscopic constant
=::.
4. Osmotic Pressure (7t)
•
minimum pressure required to prevent osmosis
n = MRT
where: M = molarity; R = gas constant and T = absolute temperature
68
Physical and Chemical Principles
Physical Chemistry
For solution of electrolytes, there is an increase in the number of particles due to
ionization. To account for this increase, the use of Van ' t Hoff factor, i, in the equations
above is required. The Van 't Hoff factor "may also be related to the degree of dissociation
a) of the electrolyte
i- 1
a= - v- 1
where: v = number of ions formed upon dissociation of one molecule of the electrolyte
Electrochemical Cells
A . Types of Electrochemical Cells
1. Galvanic cell - produces electricity as a result of the spontaneous reactions
occurring inside it where the cathode has a higher potential than the anode
2. Electrolytic cell - non-spontaneous reaction is driven by an external source of
current. They have a common electrolyte and no salt bridge.
• Reduction occurs at the cathode and oxidation occurs at the anode
• However, in electrolytic cells, electrons are forced to flow from the anode to
cathode
• In electrolytic cells the anode is positive and the cathode is negative
• In galvanic cells the anode is negative and the cathode is positive
3. Cell Reactions
• reactions in the cell written on the assumption that the right hand electrode is the
anode
----..___
Zn(s) I ZnS04(aq) II CuS04(aq)I Cu(s)
Their reduction half-reactions are
zn+2(aq) + 2e- -+ Zncsl
Left:
Right:
Cu +2(aq) + 2e- -+ Cu(s)
2
Overall:
Cu+2(aq) + Zil(sJ -+ Cll(sJ + zn+ cav
::.lectrolysis
A redox reaction brought about by the passage of a direct current through a solution
of an electrolyte
In electrolytic conduction, the following phenomena occur:
a. Mass Movement of Ions
• cations migrate to the cathode while anions migrate to the anode
• migration involves not only transfer of electricity from one electrode to"the
other, but also a transport of matter from one part of tJ:ie conductor to the
other
b. Occurrence of Oxidation-Reduction Reactions
Typical example is t4e electrolysis of aqueous Na OH
Anode:
2 Ho- 1 -+ 2 W + 02 (gJ + 4eCathode:
2 W(aq) + 2e- -+ H2(g)
1
Overall:
2 0Ir (aq) + 2ll(aq) ~ 0 2(g) + 2 H2(g)
~araday's
Law
The mass of a substance involved in the reaction at the electrode is proportional to the
quality of electricity passed through the solution
Consider the reaction:
69
Physical and Chemical Principles
Physical Chemistry
Q = It =
mM
(MW)M
x
nmolexmolM
x
F
where: Q = amount of charge [CJ, I = current [A] , t = time [s] , and F, Faraday's
constant = 96500 C-(mol eT 1
Phase Equilibria
1. One-Component Systems
• May consist of one phase, two phases or three phases
• For systems with more than one phase, the chemical potentials in the different
phases must be equal to each other
dP
iiHm
= -a. Clapeyron Equation
dT TliVm
Governs the temperature dependence of pressure in a two-phase, onecomponent system
dP iiH vap/sub dT
b. Clausius-Clapeyron Equation
p
R
T2
Gives the relationship between pressure and temperature for a two-phase, onecomponent system assuming that the vapor phase is ideal and the molar volume
of the condensed phase is negligible compared to that of the vapor phase
LiH
c. Trouton 's Rule ~ = 88 J - mo1- 1 - K- 1
Ts
Used to estimate the 'molar enthalpy of vaporization of liquids
2. Ideal SolutiOJ!S
• Solutions with heat of mixing equal to zero and the volume of the solution is the
sum of the volumes of the components of the solution
•
Raoult's law: PA = x A P~
where: PA = vapor pressure of component A in the solution, xA = mole fraction
and PA0 = vapor pressure of pure A
•
For miscible systems, PT =
n
LP;
i=I
•
3. Real Solutions
• Governs mixtures of volatile solutes in dilute solutions
• Henry's Law: PA = Kx A
70
Physical and Chemical Principles
Physical Chemistry
REVIEW QUESTIONS AND PROBLEMS
l. Which of the following statement is CORRECT about ideal gas?
a. The pressure of the gas is equal to the total kinetic energy of the molecules in
. a unit volume of the gas
b. The product of pressure and volume of the gas is always constant
c. The average kinetic energy of molecule of the gas is proportional to its
absolute temperature
d. The average kinetic energy of molecule of the gas is propbrtional to the
square root of its absolute temperature
For numbers 2 and 3 ...
A gas mixture has a density of 1.0628 g/L at 30°C and 740 torr.
2. What is the possible component of the mixture?
a. C0 2 (44)- 0 2 (32)
c. He(4)- NH 3 (1 7)
d. Ar (40)- Kr (84)
b. Ne (20) -Ar (40)
3. What is the fraction of the lighter gas in the mixture?
a. 0.18
b. 0.36
c. 0.64
d. 0. 82
~
.
4. For ideal gas possessing only translational energy, the following relationships are
valid except
a. Cp = 2.5 R
b. Cp = Cv - R
c. Cv = 1.5 R
d. CJ Cv = 1.67
- Calcium carbonate decomposes upon heating to form C0 2 gas according to the
follo wing reaction:
CaC03(s) -+ CaOcsl + C02cg>
What volume of C0 2 gas collected over water at 25°C and 740 mm Hg is obtained
from 2.875 grams of CaC0 3? Molar mass ofCaC0 3 = 100 g/mol and Vapor pressure
of H 20 at 25 °C = 23 .756 mm Hg
a. 0.69 L
b. 0.72 L
c. 0. 75 L
d. 0.78 L
6. Which of the follo wing exist as gas at room temperature?
a. Br2
b. Ga
c. 12
d. none of these
For numbers 7 and 8...
The following data were obtained from the molecular weight determination of a
mixture of CO and C0 2 using Regnault's Method at 25 °C and 1 atrn:
37.2564 grams
weight of dry bulb
37.5265 grams
weight of bulb + CO-C0 2 mixture =
weight of bulb + H 20
215.8819 grams
- What is the average molecular weight of the mixture?
a. 31 g/mol
b. 37 g/mol
c. 43 g/mol
What is the mole percentage of C0 2 in the mixture?
a. 0.22
b. 0.28
c. 0.44
d. 49
g/~ol
d. 0.56
9. Absolute zero maybe regarded as that temperature at which
a. alt gases become liquids
c. alt substances are solids
b. molecular motion ceases
d. water freezes
I . The simplest state of matter is _ _ _ __
a. solid
b. liquid
71
c. gas
d. plasma
Physical Chemistry
Physical and Chemical Principles
11. At what temperature will the velocity of C0 2 molecules equal the velocity of oxygen
molecules at 0°C
a. 102°C
b. 632°C
c. 132°C
d. 125°C
For numbers 12and13 . ..
The density of a saturated hydrocarbon containing 80% \Vt carbon was measured
against pressure at 20°C according to the following data:
(o--L- 1
0.298
0.692
1.188
1.784 2.49.1
P (atm)
0.2
0.4
0.6
0.8
1.0
12. What is the exact molecular weight of the gas·eous hydrocarbon?
a. 29.675 g-mor 1
c. 30.891 g-mor 1
1
b. 30.187 g-mor
d. 31.042 g-mor 1
13. What is the molecular formula of the gas?
a. CH4
b. C2H6
c. C2H2
14. Nitrogen gas escapes through a pinhole in 68.4 seconds. Under the same conditions,
a gaseous compound with the empirical formula CH 2 escapes in 83.8 seconds. What
is its molecular formula?
a. C 2H4
b. C3H6
c. C~s
d. CsH1 0
exist
15. If a given gas has a compressibility factor, Z > 1, this means that
between the molecules of gases
a. attractive forces
c. negligible forces of attraction
b. repulsive forces
d. negligible repulsive forces
16. The van der Waals constants a and b for Ne gas are 0.02138 Pa-m6-mor 2 and
l.709x 10- 5 m 3-mor 1, respectively. What is the critical temperature (K) of the gas?
a. 10
b.'25
c. 30
d. 45
17. Generally, viscosity of gases _____ as temperature increases.
c. approaches unity
a. remains constant
d. decreases
b. increases
18. For a compressible fluid, .the pressure head in the Poiseuille equation is replaced by
?
the expression: t.P
= pi- -
?
P[ where Pi = initial pressure, Pr = final pressure and P0 =
2P0
pressure at which volume was measured. If the inlet and outlet pressures of the gas
were 1.100 bar and 1.090 bar,respectively, what is the viscosity (µP) of 200-mL o~
Ar gas measured at 30°C and 0.95 bar which required 10 sec to flow through a 500cm tube of 0.5-mm radius?
a.0.70
b.1.40
c. 2.10
d.2.80
19. Fluids whose viscosity increases as shear rate increases.
a. Dilatant
c. Newtonian
b. Pseud astic
d. Bingham plastic
20. The temperature dependence of the viscosity of a gas is given by the expression:
· { - L':.Eviscosity )
µ = A ex
RT
where t.E =heat of viscosity (kJ-mor 1) and A= constant
72
Phy
Physical and Chemical Principles
Physical Chemistry
The following data were obtained for the viscosity of glycerine as a function of
temperature:
t °C
--45
-25
-10
0
20
30
µ(Pa-s)
· 7010
263
35
12
1.5
0.7
Calculate the viscosity of the gas (Pa-s) at 25°C
a. 0".90
b. 0.94
c. 0.96
d. 0.98
21. Fluids whose viscosity increases with time at constant shear rate.
a. Inviscid
b. Rheopectic
c. Thixotropic
d. Pascalian
22. Silver crystallizes with a face-centert'.d cubic unit cell. The radius of a silver atom is
0.144 run. Calculate the density of solid silver. Ag (107 .87 g/mol)
a. 24.8 g/mL
b. 21.2 g/mL
c. 15.7 g/mL
d. 10.6 g/mL
23. What happens to the molecules in a liquid when the liquid is heated and vapor starts
to form?
a. the intramolecular forces between liquid molecules are disrupted
b. the intermolecular forces between liquid molecules are disrupted
c. kinetic energy is removed from the system
d. London forces become stronger
_4. Fe crystallizes in a body-centered cubic lattice. The density of iron is 7.86 g/cm3 .
Calculate the atomic radius of iron in angstrom.
a. 1.24 A
b. 2.48 A
c. 0.62 A
d. 2.02 A
_5. One colligative property of solutions is its freezing point depression. Which
observation will show that the solute is an electrolyte (b.Tr/m)?
a. is not a constant
c. is less than Kr
b. is not Kr
d. is greater than Kr
- 6. A 0.2 m aqueous solution ofKCl freezes at- 0.680°C. The osmotic Pat 0°C is
a. 9.8 atrn
b. 16.3 atrn
c. 8.2 atm
d. 10.8 atrn
Which of these 0.1 m solutions will give the highest boiling point at 1 atm?
a. table salt solution
c. barium chloride
d. potassium chloride
b. sugar sol!1tion
A solution of 0.72% wt HCl, freezes at -0.706°C. Calculate the apparent molecular
weight ofHC!.
a. 38.2 g/mol
b. 37.8 g/mol
c. 37.1 g/mol
d. 36.5 g/mol
~la! solution ofK3Fe(CN)6 freezes at-0.062°C. What is its apparent degree
of dissociation?
a. 25 .9%
.=o.
b. 47.2%
I
c. 67.2%
d. 78%
.
All the half-cell ?otential (£0 ) use the _ _ as the reference.
a. Hydrogen
electrode
c. carbon half-cell
f
b. oxygen half-cell
d. arbitrarily net zero point
.: l. An electrochemical cell in which chemical reaction is forced to occur by the
application of an outside source of energy is
a. galvanic
b. electrolytic ·
c. electrical
d. chemical
The more negative the value of£0 , the more likely the reaction is to proceed from
a. left to right
b. right to left
c. either way
d. can't be determined
73
Physical Chemistry
Physical and Chemical Principles
33. Which of the following statements about colligative properties is TRUE?
a. Both vapor pressure and freezing point INCREASE when a non- volatile
solute is added to a solvent.
b. Both freezing point and boiling point INCREASE when a non- volatile
solute is added to a solvent.
c. Both vapor pressure and boiling point DECREASE when a non- volatile
solute is added to a solvent.
d. Colligative properties depend only upon the NUMBER of solute particles in
a solution and not upon their identity .
..
34. Consider the following standard reduction potentials,
Half Reaction
e0 , V
Fe +(aq) + e- =+ Fe-+(aq)
0.77
H20 2(agl + 2e- =+ 20H- (agl
0.88
.
For the voltaic cell reaction below, calculate the Fe2+ concentration (in M) that
would be needed to produce a cell potential equal to 0.16 V at 25°C when (OH-) =
0.10 M, (Fe 3+)=0.50 M and (H 20 2) = 0.35 M.
a. 0.20 M
b. 0.40 M
c. 0.60 M
d. 0.80 M
35. A d~cidic aqueous . solution of Na2S04 is electrolyzed between platinum
electrodes for 3.75 hrs with a current of 2.83 A. What volume of S02 gas, saturated
with water vapor at 25°C and at a total pressure of742 mm Hg would be collected at
the anode?
a. 1.281 L
b. 2.562 L
c. 5.124 L
d. 10.248 L
36. An aqueous solution of gold nitrate is electrolyzed with a current of 0.555 ampere
until 1.32 g of Au has be"en deposited on the cathode. If the atomic weight of Au is
197, determine the duration of the electrolysis.
a. 65.43 min
b. 23.67 min
c. 58.28 min
d. 60.00 min
37. The vapor pressure of a liquid
a. always increases with temperature
b. always decreases with temperature
c. is independent of temperature
d. none of these
38. A solvent- water mixture is to be distilled at 95°C. The vapor pressure of the solvent
at this temperature is 130 mmHg and that of water is 640 mmHg. The solvent is
immiscible in water and has a molecular weight of 150. The weight of the solvent in
kilograms that will be carried over in the distillate with 200 kg of water is
a. 358.73
b. 423.57
c. 338.54
d. 524.63
39. The law relating the solubility of the gas to its pressure is called
a. Raoult's Law
c. Henry's Law
b. Distribution Law
d. Arrhenius' Law
40. The vapor pressure of solid C0 2 is 76.7 mm Hg at -103°C and its normal
sublimation point is -78.5°C. What is the heat of sublimation of C0 2?
a. 6061 cal/mo!
b. 6160 cal/mo!
c. 6610 cal mole
d. 6801 cal/mo!
41. Dry air is bubbled. through 25.0 liters of water at a rate of 15 L (STP)/min. The air
leaving the liquid is saturated with water at 25°C and 1.5 atm. How long will it take
for all the water to vaporize?
a. 32.9 days
b. 67.8 days
c. 79.1 days
d. 80.7 days
74
Physical and Chemical Principles
Physical Chemistry
42. Ethanol is to be used in an automobile carburetor that is adjusted to give a 9:1 airfuel ratio (mass ratio). If the temperature in the manifold is 60°F and the pressure is
atmospheric. What percentage of the alcohol will be evaporated assuming that
· equilibrium between vapor and liquid is reached? Vapor pressure of ethanolat 60°F
is 33.75 mm Hg
a. 56%
b. 76%
c. 66%
d. 90%
43. When gaseous ammonia is dissolved in water, the resulting solution does not obey
Henry's Law. Which of the following best explains why this solution does not obey
Henry's Law?
a. All of the NH 3 that initially dissolves in the water rapidly escapes from the
solution because NH 3 is a gas at room temperature
b. NH 3 reacts with the solvent to produce ammonium and hydroxide ions
c. NH 3 is not soluble in water because it is a non-polar molecule.
d. The hydrogen bonding between ammonia molecules is so strong that NH 3
cannot be dissotvf in water.
44. PCls(g) dissociates into PC1 3(g) and Cl 2(g) when heated at 250°C and 1 atm. If the
density of the gas mixture at equilibrium is 4.4 g/L, the fraction of PC15 (g)
dissociated is
• a. 0.103
b. 0.328
c. 0.725
d. 0.209
..t5. For the process C(s) + 0 2(g) !:::; C0 2(g), it is found that t.G at a given temperature is 10 kcal/mole. Which statement is correct at this temperature?
a. The system is in equilibrium
c. C0 2 will decompose spontaneously
d. The process will proceed reversibly
b. C0 2 will be formed spontaneously
6. At 3000 K and 1. atm, C0 2 is 40% dissociated to CO and 0 2 , according to the
reaction: 2 C0 2 (g) !:::; 2 CO (g) + 0 2 (g)· Its percentage dissociation when the pressure
is increased to 2 atm is
b. 0.335
c. 0.425
d. 0.375
a. 0.350
For a chemical reaction in a state of equilibrium, a decrease in temperature will
a. favor the reaction that is exothermic
b. favor the reaction that is endothermic
c. have no effect on the system
d. increase the equilibrium constant of the system
~8.
The dissociation constant for liquid water into hydrogen and oxygen gas at 1227°C
is 1.90 x 10- 11 and it is 3.90 x 10- 19 at 727°C. The heat of reaction of the following
reaction is: H2cgl + Yi 0 2cg) !:::; H20 (1)
a. - 442 kJ/mol
b. - 221 kJ/mol
c. 221 kJ/mol
d. 442 kJ/mol
.:.9, In a chemical reaction, equilibrium has been established when the _ _ _ __
a. opposing reaction ceases
c. reaction ceases to generate heat
b. concentrations are equal
d. net velocities of reactions is zero
:o. For the reaction: 0
2 O(g)
In Kp = - 27.55 at 900 K
llH = 67,850 + l.85T-0.32lx!0- 3 T 2 [=)cal/mo!
Find the extents to which 0 2 cgJ will be dissociated into atoms at a temperature of
4000 K at 1 atm.
d. 90%
a. 60%
b. 70%
c. 80%
2 cgJ
!:::;
75
/
Physical and Chemical Principles
Biochemical Engineering
E. BIOCHEMICAL ENGINEERING
.....
~~~~~~~~~~~~~~
Biochemical Engineering
• deals with the conduct of biological processes on an industrial scale
· • deals with the processes where the catalysts are either living cells or extracts from
them
Bioengineering
• engineering that involves with the biosynthesis of animal or plant products
• application of engineering knowledge to tfie field of medicine and biology
Products from Microbial Processes
Human Health Care
Animal Health Care
Antibiotics
Antibiotics
Hormones
Hormones
Drugs
Vaccines
Industrial Chemical
Agricultural Chemical
Pesticides
Acetone
Butanol
Herbicides
Fungicides
Lactic Acid
Plarit Growth Hormones
Citric Acid
Lactic Acid
Ethanol
Glycerol
Foods and Beverages
Alcoholic Beverages
Vinegar
Glutamic Acid
Cheese
Soy Sauce
Specialty Chemical
Vitamins
Amino Acid
Enzyme
Classification of Organisms
1. According to structure
a. Procaryotes - cells without nuclear envelopes
b. Eucaryotes - cells with nuclear envelopes
2. According to carbon sourc~
a. Autotrophs - uses carbon 'di~ide as their carbon source
b. Heterotrophs - uses fancier carbon compounds such as glucose, ethanol and
sucrose as carbon source
3. According to energy source
a. Chemotrophs - obtain energy by breaking down substrate
• Chemoorganotrophs - break down organic compounds
• Chemolitotrophs - break down inorganic substrates
b. Phototrophs - obtain energy from light
• Photoorganotrophs - uses light as energy source and organic substances as
carbon source
• Photoautotrophs - uses light as energy source and carbon dioxide as principal
carbon source
4. According to final electron acceptor
a. Aerobes - organisms that use molecular oxygen as final oxidizing agent
b. Anaerobes - organisms that do not need oxygen but instead use nitrates, sulfides,
carbon dioxide as their oxidizing agent
c. Facultative Anaerobes - organisms that are able to grow in the presence or
absence of molecular oxygen
d. Microaerophiles_- microorganisms that need only a little amount of oxygen that is
lower than atmospheric concentration
76
Physical and Chemical Principles
Biochemical Engineering
Lipids
• comes from the Greek word, lipos, which means fat
• water insoluble biomolecules highly soluble in organic solvents such as chloroform
and ether
• used as fuel molecules, energy storage and component of membranes
A. Fatty Acids
• stored as triacylglycerols or glycerides and used for energy storage
• found in the cytopl asm of adipose cells
• triacylglycerols are oils of plants and fats of animals
• triacylglycerols that are liquid at room temperature are called oils and those that
are solid at room temperature are generally called fats
1. Occurrence
• most natural fatty acids have unbranched chains and contains even number of
carbon ato'ms
• first double bond occurs between C-9 and C-1 0
• remaining double bonds begin at C12 and C15 and are therefore not
conjugated
2. Common fatty acids
a. Saturated fatty acids
• Laurie Acid (dodecanoic acid)
• Myristic Acid (tetradecanolc acid)
• Palmitic Acid (hexadecanoic acid)
-----stearic Acid (octadecanoic acid)
b. Unsaturated fatty acids
• Palmitoleic Acid ( cis-9-hexadecenoic acid)
• Oleic Acid (cis-9-octadecenoic acid)
• Linoleic Aci'\( cis,cis-9, 12-octadecenoic acid)
• Linolenic Acid\( cis,cis,cis-9, 12, 15-octadecatrienoic acid)
3. Terpenes and Terpenoids
• important constituents of essential oils
• produced by a variety of plants particularly conifers
• derived from isoprene-(2-methyl-1,3-butadiene)
Monoterpenes
Sesquiterpenes
(contains 10 carbon atoms)
(contains 15 carbon atoms)
~
~~
~
Myrce11e
a-Farnesene
(isolated from bay oiJ)
(from natural coatino- of a Jes
CH 3
CH 3
CH 1
/!-carotene (source of two molecules ofVitamin A)
77
Physical and Chemical Principles
Biochemical Engineering
C. Steroids
•
•
•
derivatives perhydrocyclopentanophenantherene ring system
important biological regulators that shows dramatic physiological effects when
administered to living organisms
important steroids are male and female sex hormones, adrenocortical hormones. D
vitamins, bile acids and cardiac poisons
1. Cholesterol
•
•
•
.•
•
most widely occurring steroids extracted from animal tissues
first isolated in 1770
Windaus and Wieland outlined the structure of cholesterol
Intermediate in the synthesis of all of the steroids in the body
High levels of cholesterol in the body causes arteriosclerosis and heart ai:raz
prq:nane
cholilne
I
2. Sex hormones
•
•
•
classified into to three major groups: estrogens, androgens and progestins
the first sex hormone isolated was an estrogen by Butenandt (UG) and Doi=:
(SLU) from the urine of a pregnant women
the true female hormone, estradiol was isolated by Doisy from 4 tons of so .
·
ovaries (12 mg)
HO
estradiol
•
•
Butenandt and Tscherning isolated androsterone (15 mg) from 15,000L o:
male urine
Laqueur isolated the true male hormone, testosterone from bull testes which is
responsible for the growth of facial and body hair, deepening of the voice.
muscular development and maturation of the male sex organ
Jestqsterone
78
Physical and Chemical Principles
•
Biochemical Engineering
Progesterone is the most important pregnancy hormone secreted by the
placenta
3. Adrenocortical hormones
• isolated from the adrenal cortex and are apparently involved in carbohydrate,
proteins and lipid metabolism, water and electrolyte balance and reactions to
allergic and inflammatory phenomena
~.
Prostaglandin
• C20 carboxylic acids that contains a five membered ring, at least a double bond
and several oxygen-containing functional groups
• first isolated from seminal fluid
• known to affect heart rateJ212._od pressure, blood i;lotting, conception, fertility and
allergic responses
COOH
.§'....•·
HO
Amino Acids
• building blocks of proteins
only 20 of 22 amino acids are found in majority of organisms
l. Neutral Amino Acids
H2
I
H-CH
\ c=o
I
79
Biochemical Engineering
Physical and Chemical Principles
Phenylalanine (Phe)" • F
lsoleucine (1le)' - I
Leucine (leul - L
H
· 1~
HiC-·-·
H:zN
\
I
1/- 01:!
A.sparagine (Asn) - N
CH
01
\
HO
Gl11tamine (Gln) - Q
Serine (Ser) - S
Proline (Pro) - P .
I
I
OH
c= o
NH
/c=o
0
NH2
c~I
Threonine (Thrt- T
0
II
H O 'O
'
CH2
\ CH-
-
I
H2
,,.c........_ /c,
NH2
HO_,.
er
"SH
HO- C
"
NH2
Tyrosine {Tyr) - Y
Cvsteine (Cys)- C
Proline (Pro) - P
2. Acidic Amino Acids
I
Glutamic Acitl GJu) - E
Aspartic Acid (Asp) - D
3. Basic Amino Acids
H
H,
H2N"-.
/
C
H,
H,
c"-. /
C
H,
NH2
c"-.1
CH
I
c= o
NH
II
H,
N
C
H
H,
I
I
CH
I
OH
Arginine (Arg) - R
80
J.
NH,
c= o
I
OH
L}'sine (Lysl- K
H,
H2N- c......_ /c......_ /c......_
N'-....
(
c-
_jJ
N'
H,
c
NH2
1
"-.CH
I
I
OH
c= o
Histidine (His/- D
Physical and Chemical Principles
Biochemical Engineering
Carbohydrates
• general formula C 0 (H20) 0
• polyhydroxy aldehydes and ketones
• Monosaccharides - simplest carbohydrates that cannot be hydrolyzed into simpler
carbohydrates
• Disaccharides - carbohydrates that undergo hydrolysis to produce only two
molecules of monosaccharide
~~-
Classification of Monosaccharides
1. According to the number of carbon atoms present
o~c / H
l (R)
H-
C-
H-
C-
OH
I(R)
OH
I
tetrose
2. According to functional group present, whether aldehyde or ketone
O~ /H
c
I
I
H-C-OH
H--C-OH
I
CH OH
a/do.fie
3 . D and L Designations of Monosaccharides
O~
O~/H
/H
~c'
O~
~c'
:
I
I
:
I
I
CH20H
H-C-OH
I
I
I
:
I
~-----------------j
HO-C-H
HO-C-H
I
: H-.C.-oH :
I
I
I
I
I
I
I
H-C-OH
/H
r--------=---------1
I
c
H-C-OH
H-C-OH
r-------=--------~
1
:
: H_..C._OH :
:
I
:
CH 20H
I
I
:
I
I
I
t________________ J
D- lucose
81
r--------r-------;
: HO_..C._H
::
I
I
CH20H
:
::
:
~----------------J
Physical and Chemical Principles
Biochemical Engineering
C. Th e D F amuy
'I o f Aid 0 h exoses
~c
HO-C-H
.
H-C-OH
lrsJ
HO-C-H
lrsJ
H-~-OH
H- ~ -OH
; (R)
. ~ (R)
H-C-OH
H-c-oH
I
..
I
CH20H
O~
H-C-OH
l (R)
H-C-OH
D-Allose
I
I
I
lrsJ
l (R)
I
~c
~c
H-C-OH
l (R)
O~ / H
O~/H
O~ / H
...,H
l (R)
; (R)
D-Mannose
O~/H
O~/H
H-C-OH
LR)
lrsJ
HO-C-H
H-C-OH
l (R)
l (R)
HO-~-H
HO-~-H
I
CH20H
»-Glucose
l (R)
H-C-OH
lrsJ
H-C-OH
~c
~c'
lrsJ
HO-C-H
H-C-OH
I
·'
Ls)
HO-C-H
H-·-~-OH
CH20H
~
~c
H-w-OH
CH20H
.
O~/H
~c
lrsJ
HO-C-H
lrsJ
HO-C-H
. l (R)
HO-.Q-H
; (R)
; (R)
; (R)
H-C-OH
H-c-oH
H-c-oH
I
I
CH20H
CH20H
D-Galactose
I
CH20H
1'-Talose
D. Disaccharides
I. Sucrose
• found in all photosynthetic plan!L• obtained commercially from sugarcane
• acid catalyzed hydrolysis yields I mole ofD-glucose and I mo! D-fructose
• a non-reducing sugar (negative to Fehling' s test)
Co"1
CH20H
CH 20H 0
~~O~H20H
OH
OH
2. Maltose
• Obtained from the hydrolysis of starch using diastase
• acid catalyzed hydrolysis yields 2 moles ofD-glucose
• a reducing sugar (positive to Fehling's test)
• a -glycosidic linkage
82
j
Physical and Chemical Principles
Biochemical Engineering
3. Cellobiose
• Obtained from partial hydrolysis of cellulose
• acid catalyzed hydrolysis yields 2 moles ofD-glucose
• a reducing sugar (positive to Fehling' s test)
• ~-glycosidic linkage
4. Lactose
• Present in the milk of humans, cows and almost all other mammals
• acid catalyzed hydrolysis yields D-glucose and D-galactose
• a reducing sugar
• ~- glycosidic linkage
~O"v;~H
~
OH
OH
Enzymes
/
• biocatalysts that lower the activation energies of important reactions without altering
the reaction equilibria
• specific proteins that enhance biochemical reactions
• highly specific in their substrates
-~
Sources - plant, animal organs, microbial cells
3 . Types of Enzymes
1. Endoenzyme or Intracellular enzyme
2. Exoenzyme or Extracellular enzyme
General Properties of Enzymes
1. Enzymes are proteins
2. Enzymes have electrical charges which depends on the pH and two pK v.alues
3. Enzymes have four definite dimensional structures:
a. Primary structure - amino acid sequence of the polypeptide chain (most
important and specific structure; determines secondary and tertiary structures)
b. Secondary structure - spatial arrangement of polypeptide chains into helices,
pleated sheet and random coil structures
.
c. Tertiary structure - three dimensional arrangement of helices, pleated sheet
and random coil structures in enzyme
d. Quaternary structure - aggregation of enzyme submits or molecules into
multi-submit or multi-enzyme complexes.
83
Biochemical Engineering
and Chemical Principles
" on-covalent bonds that contribute to the four dimensional structure of enzymes:
c. Hydrogen Bond - Interpeptide Hydrogen Bond; Side Group Hydrogen Bond
d. Ionic Bond (Electrostatic Attraction)
e. Non-polar Side Chain Interaction (Hydrophobic Bond)
f. Polar Side Chain Interaction
D. Six General Classes of Enzymes and Functions
(Commission on Enzymes of The International Union of Biochemistry)
1. Oxido-reductases - oxidize or reduce substrates by transferring hydrogen or
electrons
2. Trans/erases - remove groups (excluding hydrogen) and transfer them to acceptor
molecules (excluding water) ; transfer of groups
3. Hydro lases - for hydrolytic reactions. It catalyzes the splitting of a covalent bond
of the substrate and that of a water molecule with the subsequent addition of the
hydrogen and hydroxide to the two fragments of the substrate molecule
4. Lyases - remove groups from the substrate by hydrolysis to form a double bond
or conversely, add groups to the double bonds
5. Isomerases - catalytic isomerizations. It causes isomerization to the substrate
6. Ligases or Synthetases - cause condensation of two molecules by splitting a
phosphate bond
E. Factors Affecting Enzyme Catalyzed Reactions
1. Enzyme Concentration
2. Substrate Concentration
3. Product Concentration
4. Inhibitor Concentration
5. pH and Ionic Strength
6. Temperature
(
F. Enzyme Theories
1. Lock and key theory (Emil Fischer) - illustrates the precise fit between enzyme
and substrate.
2. Induced fit theory (Koshland) - enzyme undergoes structural or conformational
changes brought about or induced by the substrate.
3. Michaelis-Menten Theory - enzyme activity depends on substrate concentration.
• popular model for enzyme kinetics
• plot of reaction velocity and substrate concentration
• consist of fi rst order, combination of zero-first order and a zero order part
vmaJs]
v = K m_+[S]
where: V=velocity of enzymatic reaction, Vm=limiting (maximum) velocity,
S=substance concentration, Km=M ichaelis-Menten constant
a. At low substrate concentration .. . KM>> [S]
v = vmax
[S]
KM
Reaction is apparent 1 st order in the substrate concentration
84
G
Biochemical Engineering
Physical and Chemical Principles
b. At high substrate concentration ...KM<< [S]
v = vmax
Reaction is apparent 01h order in the substrate concentration
c. When the reaction rate is half the maximum rate
Vmax
Vmax [SJ
h
v = -2- = K m +[s] t en K M=
[ ]
s v=Yivmox
G. Evaluation of Michaelis-Men ten Constant
Lineweaver-Burke
Plot
I
Hanes-Woolf
Plot
s
I
- vs. v
s
plot ofx vs. y
-rs
S/-r5
KM
KM
Vmax
Vmax
1/S
1
---
Vmax
---
l /-r5
mmoVL mmo l/L-s
s
---
Vmax
1
y-intercept
v
- vs. v
- vs.S
v
1
KM
slope
Eadie-Hofstee
Plot
-rsfS
vmax
KM
Type of Pl ot
K-'1
vmn
Lineweaver-Burke Plot
1.7895
0.8792
0.300
0.126
7.9 365
2.3810
0.4200
Hanes-Woolf Plot
1.7456
0.8627
0.450
- 0. 177
5.6497
Eadie-Hofstee Plot
0.6786
0.5800
0.600
0.224
4.4643
0.750
0.255
3.9216
0.900
0.295
3.3898
~
0.3933
86
0.3733
.9412
03400
3.0508
0.3278
2.
Micha elis-Menten Pl ot
Lineweaver-Burke Plot
' -----------------------.----- ---
OJS - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .
I
0.30
/
0.25
71)
010
0.15
0.10
!
Y""2.0354x + 1.1374
l
R'=0.9993
•
0.05
0.00
0.00
0.20
0.4-0
0.60
0.8'!
0.00
1.00
o.so
1.00
1.50
2.00
2..50
3.00
3.50
I/JS!
!Si
Ead ie-H ofstee Plot
Hanes-Woolf Plot
::: -------------------\-----11,'il
0.25
0.20
if'
y"" 1.159lx + 2.0233
R2 = 0.9859
I
0100
0.4-00
0.600
0.8'!0
0.15
0.10
I
0.000
y = · I. 724x - 0.8548
R~ ='0.9T
1.000
JS!
85
0.05
I
0.00 '------~--~-~---'
0.00
0.10
0.20
0.30
0.40
0.SO
Physical and Chemical Principles
Biochemical Engineering
H. Inhibition on Enzyme Reactions
• Inhibitors are species that interact with enzymes and make the enzyme ineffective
• The most common types of reversible inhibitions include:
1. Competitive Inhibition
• inhibitor (I) competes with the substrate (S) for the enzyme molecule to form
an inhibitor (E•I) complex
Lineweaver-Burke plot
KM (i+l!l)·J_+_l_
_!_ _
v-
[S)
K1
vmax
vmax
Competitive inhibition results to increase in slope while no change in theyintercept as inhibitor concentration [I] increases
2. Uncompetitive Inhibition
• Inhibitor has no affinity for the enzyme and does not compete with the
substrate however it ties up the enzyme-substrate complex (E•S) formi~g ar.
inactive inhibitor-enzyme-substrate complex (E•I•S)
vmax
[S]
v =---~---
KM +(S{l+ 2; J
Lineweaver-Burke plot
/
1
KM
1
v
Vmax
[SJ
- = - - ·-
l+l!l
K
1
+ ---
Vmax
Uncompetitive inhibition results to increase in y-intercept while no change ir.
the slope as inhibitor concentration [I] increases
3. Non-competitive Inhibition
• Substrate and inhibitor react with different active site of the enzyme
• Deactivating complex is formed by two reversible reaction steps:
a. After the enzyme-substrate complex (E•S) is formed, the inhibitor attaches the enzyme at the inhibitor site (I•E•S)- KAi
b. After the enzyme-inhibitor complex (E•I) is formed, the substrate attaches -the enzyme at the substrate site (I•E•S) - Kci
v
=
vmax
[S)
---,---~~---,.---.,-
KM (1+J!LJ+[s](1+J!LJ
KAi
Kci
For mixed non-competitive inhibition ... K ai -:t Kci
For pure non-competitive inhibition . . . Kai= Kci
86
Physical and Chemical Principles
Biochemical Engineering
Lineweaver-Burke plot
_!_ = K M
v vmax
1 [I] )
(l+_N_) ·~+ + ~
(
K Ai
[S]
Vmax
on-competitive inhibition results to increase in both slope and y-intercept as
inhibitor concentration [I] increases
I.
Chemostats
• Essentially CSTRs containing
microorganisms
• Used to control cell growth rate
by adjusting the dilution rate
• In most systems, the entering
microorganism concentration is
set ta zero (Ceo = 0)
vo, Cso, Ceo
lt
v
v, Cs, Cc
Cell balance
Rate of cell ] = [ Cells inlet ] _ [ Cells outlet] + [Net rate of live]
[ accumulation
flo w rate
flow rate
cell generation
V dCc = v0 Cco - vC c + v(r
rd)
"
dt
eglecting death rate and since entering microorganism concentration is set to zero . . .
0
V dCc =
dt
-
-vCA
Yr
~ '
g
Using the Monod equation, the growth rate is given by the equation
r = µC
g
c
= µ max Cs C
K +C
c
s
s
where rg = cell growth rate [g-L- 1-s- 1] , µ = specific growth rate [s- 1] , Cc = cell
concentration [g-L- 1] ; µmax = maximum specific growth rate [s- 1] , Cs = substrate
concentration [g-L- 1] and Ks = Monod constant [ -L- 1
dC c
V - - = µC c V - vCc
dt
Substrate balance
Rate of substrate ] = [ Substrate inlet] _ [ Substrate outlet ] + [Net rat~ of substrate ]
[ accumulation
flow rate
flo w rate
generation
dCs
V - - = v0 Cso - vC 5 +rs V
dt
For a steady state operation and ~v_=_v~0~'---~
f
~=DI
Cell balance
Iµ =
Substrate balance
I-rs = D(C
=
87
80 -
Cs)
I
Biochemical Engineering
Physical and Chemical Principles
REVIEW QUESTIONS AND PROBLEMS
1.
These are the most abundant organic molecules in living cells
a. proteins
b. carbohydrates
c. lipids
d. fats
2.
Type of bacteria that are considered to be ancient organisms such as methanogens,
halobacteria and the1moacidophiles
a. archaebacteria
c. bacteriophage
b. eubacteria
d. virus
3.
Which of the following is not a steroid?
a. sex hormones
b. cholesterol
c. adrenocortical hormones
d. prostaglandin
4.
In an experiment conducted to evaluate the Michaelis-Menten constant, it was found
that 1 g of bacteria could decompose the waste at a maximum rate of 35 g-day- 1
when the waste concentration was high. It was also found that the same quantity of
bacteria would decompose waste at a rate of 18 g-day- 1 when the waste
concentration was 20 mg-L- 1• Calculate rate of waste decomposition by 2 g of
bacteria ifthe waste concentration were maintained at 8 mg-L- 1•
a. 10.4 g-day- 1 •
b. 15.6 g-day- 1
c. 20.8 g-day- 1
d. 31.2 g-day- 1
5.
Bacteria which convert alcoholic solution to vinegar are _ _ _ __
a. coli
b. acetobacters
c. bacilli _
d. proteins
6.
The biological decomposition of organic matter accompanied by the production of
foul smelling products in an anaerobic condition is
a. pollution
b. putrefaction
c. dissolution
d. stabilization
7.
A waste treatment process by which biologically active growths are continuously
circulated with incoming biodegradable waste in the presence of oxygen is
a. activated sludge process
c. agitation process
b. stabilization process
d. trickling filter process
8.
The temperature at which a microorganism is killed within a periefc!OfiO minutes.
a. SCP
b. TDP
c. TDT
d. ATP
9.
The enzymatic hydrolysis of an ester occurs according to the following reactions:
0
0
II
c
R,.......
+
H 20
II
enzymes
........._OR
+
c
R,.......
ROH
........._OH
The following data on the rate of fo1mation of the ester at 25°C and pH = 6.5 were
obtained:
Substrate concentration,
6.0
3.0
4.5
7.5
9.0
10.5
mmol R-COOR- L- 1
Reaction velocity,
0.051
0.064
0.071
mmol R-COOH - F 1 0.079
0.082
0.091
sec- 1
The Michaelis constant, KM in millimoles per liter is
a. 4.28
b. 8.08
c. 16.8
d. 34.6
10. A visible concentrated growth of algae or other aquatic life/plants is called
b. amoeba
c. bloom
d. zoo-plankton
a: phytoplankton
11 . Materials in which microorganisms are grown in a laboratory are
b. substrates
c. enzymes
d. culture media
a. nutrients
88
Physical and Chemical Principles
Biochemical Engineering
For numbers 12 and 13 .. .
A continuously stirred tank reactor (CSTR) with a working volume of 15 m3 is used
for the production of baker's yeast. The overall reaction for aerobic fermentation is
•expressed as:
0.556 C6H 120 6 + 0.301NH 3 + 1.43 0 2 -+ 0.301 C6H1 00 3N + 2.283 H20 + 1.532 C0 2
The empirical formula for the biomass is C6H 10 0 3N (144) and molasses contains
40.8% w/v C6H 1206 (180) .
12. Calculate the daily molasses consumption to mai11tain a daily production of one
metric ton if the residual sugar in the outgoing broth is 1.4% w/v glucose.
a. 1465 L-day- 1
b. 2930 L-day- 1
c. 4395 L-day- 1
d. 5S60 L-day- 1
13. The specific growth rate of the yeast is _ _ _ __
a. 0.13 day- 1
b. 0.26 day- 1
c. 0.39 day-'
d. 0.52 day-I
14. This is the early period of growth where the organism adjusts to its new environment
a. stationary phase
c. lag phase
b. logarithmic phase
d. decline phase
15. Genetic information is stored in the structure of the DNA molecule. Which of the
following obtains the code for protein synthesis from DNA and serves as the
template for peptide formation?
a. transfer RNA
c. ribosomal RNA
b. messenger RNA
d. colon
16. It is desired to reduce the bacterial count of polluted water from 30 million
organisms per mL to 5 organisms per mL. Calculate the number of completely mixed
chlorine contact chambers in series, each having a detention time of 120 min, that
would be required ifthe fust order removal rate constant is 2.6 h- 1•
a. 3 chambers
b. 6 chambers
c. 9 chambers
d. l ~hambers
There are several forms suggested by which the hyperbolic Mfhaelis Menten
equation may be expressed linearly. If the substrate concentration, S, is plotted
against reaction velocity, V; a linear plot is obtained. The equation is called
a. Lineweaver and Burke
c. Hanes-Woolf
b. Eadie-Hofstee
d. Eisentahl and Comish-Bowden
For given species of a microorganism that doubles every 3 h, what is the mass of
biomass that may be expected from 100 liters of seed if each liter contains 8 grams
biomass and the fermentation culture was maintained for 24 h is - - - - a. 102 kg
b. 204 kg
c. 306 kg
d. 408 kg
·9. The enzyme in the stomach is _ _ __
a. urease
b. papase
c. pepsm
d. bromelis
20. The organism that reproduces by sporulation is _ _ _ __
a. bacteria
b. molds
c. protozoa
d. yeast
21. Organism that grows or uses C0 2 as its principal carbon source.
a. autotroph
b. aerobe
c. mesophile
d. heterotroph
A basic amino acid is
a. alanine
b. lysine
c. serine
d. cystein
The time to kill all bacteria in a particular culture at a specified temperature.
a. SCP
b. TDP
c. TDT
d. ATP
89
Biochemical Engineering
Physical and Chemical Principles
24. An aqueous solution of molasses contains 15% by weight sucrose (C 12 H22 0 11 ). The
C0 2 formed in the reaction can be considered as having a negligible solubility in the
solution. Determine the % wt ethanol in solution after 95% of the sucrose has been
converted to ethyl alcohol by fermentation.
a. 2.07%
b. 4.14%
c. 7.67%
d. 8.28%
25. Albizzia falcataria, a specie of plywood, after an initial thermochemical hydrolysis
yielded 25% maltose, 3% sucrose, 12% cellobiose, 43% oligosaccharides and 17%
non carbohydrates residues. The resulting hydrolyzate is passed through a column of
immobilized enzyme systems so that all types of disaccharides are converted further
to hexose units. In alcohol fermentation, the rule of thumb is 10% of the substrate is
converted· to biomass and 90% to alcohol. What mass of ethanol is expected to be
produced·per six"day week if one metric ton of pulpwood is processed daily?
b. 1223 kg
c. 1885 kg
d. 2526 kg
a. 1162 kg
26. Bacteria which grow over the temperature range of30°C to 40°C are called _ __
c. mesophiles
a. psychrophiles
b. hydrophiles
d. thermophiles
27. Group of microorganisms that grow in the presence oflow oxygen concentration are
a. pathogens .
c. fungi
b. bacteria
d. microaerophiles
28. These are very small bound particles that release digestive enzymes and contribute to
the digestion of nutrients in a cell
a. Endoplasmic Reticulum
c. Lysosomes
b. Golgi Bodies
d. Mitochondria
29. One metric ton of wild potatoes were hydrolyzed enzymically and the hydrolyzate
contained the following:
xylose
2%
glucose
16%
oligosaccharides
36%
3%
.maltose
20%
other{'
23%
pentose
It was observed that of the hydrolyzate, only maltose and glucose were fermentable
by alcohol yeast. Calculate the mass of alcohol that can theoretically be expectec
from the hydrolyzate.
a. 95 kg
b. 189 kg
c. 338 kg
d. 371 kg
30. Hydrotysis of one mole of sucrose gives
a. 1 mole of glucose and 1 mole of galactose
b. 1 mole of glucose and 1 mole of fructose
c. 2 moles of glucose
d. 1 mole of mannose and 1 mole of glucose
31 . The isoelectric point of isoleucine (2.36, 9.68) is
a. 6.02
b. 6.06
c. 5.98
d. 5.97
32. Method u~ed to free milk from disease or germs
a. Lyophitization
c. Fermentation
b. Pasteurisation
d. Putrefaction
33. The power house ofthe cell is called _ _ __
a. Nucleus
b. Mitochondria
c. Lysosone
d. Cytoplasm
34. The microorganism utilized in the production of pickles is
a. acetobacter
c. streptomyces griseus
b. lactic acid bacteria
d. aspergillus sojae
90
Physical and Chemical Principles
Biochemical Engineering
35. The color of fruit like papaya is attributed to a pigment which is a precursor of
Vitamin A. This substance is - - - - a. lecithin
b. carotene
c. lipoprotein
d. riboflavin
36. A hormone secreted by the pancreas that regulates glucose metabolism is called
~ · bile
b. insulin
c. alanine
d. cortisol
37. The disaccharide formed by~ - glycosidic bond is .
b. lactose
c. maltose
a1sucrose
d. glucose
38. In phototrophic cells, the _ _ is the organelle .-serving as the major cell power
house.
c. lysosomes
a. mitochondria
b. chloroplast
d. Golgi bodies
39. Defined as the quaritity of enzymes needed to transform 1.0 micromole of substrate
to product per minute at 30°C and optimal pH.
a. International Unit
c. Catalytic Unit
d. all of these
b. Enzyme Unit
40. The only source that naturally contains vitamin D
a. Sunlight
b. Meat
c. Fish Oil
d. Orange
1. Calculate the isoelectric point oflysine? (pKA1=2.18, pKA2 =8.95 and pKA 3= 10.53)
a. 9.74
b. 7.22
c. 6.36
42. Which of the following vitamins is water-soluble?
a. Vitamin C
b. Vitamin A
c. Vitamin D
d. 5.57
d. Vitamin E
3. It states that there is a topographical, structural compatibility b tween and enzyme
and its substrate
a. Lock and Key theory
c. Briggs-Haldane Wodel
b. Michaelis-Menten Model
d. Compatibility Theory
+i. Plarrts that are devoid of chlorophyll and are therefore unable to synthesize their own
food.
c. virus
d. none of these
a. fungi
b. bacteria
1-
The fundamental cause of sickle-cell disease is a change in the structure of
a. red cells
b. hemoglobin
c. capillaries
46. It is the major form of stored carbohydrate in animals.
a. glycogen
b. starch
c. amylose
d. blood
d. amylopectin
Which of the following is a saturated fatty acid?
a. oleic acid
c. arachidonic acid
b. linoleic acid
d. palmitic acid
A measure of the degree of unsaturation of a fatty acid
a. Acid Number
c. Saponification umber
b. Iodine Number
d. Deborah Number
- 9. These are DNA or RNA coated protein that may or may not be considered as living
things .
c. algae
d. virus
a. protozoa
b. bacteria
.:o.
Non-photosynthetic eucaryotes, highly organized with soil as its major habitat
a. fungi
b. virus
c. protozoa
d. bacteria
91
Physical and Chemical Principles
F. ENVIRONMENTAL
Environmental Engineering
EN
;...;..G
~l~
N;.;;;;;
E-=
E;..;;;
R.;.;.;.
IN;.,.;;
G_ _ _ _ _ ____.
Environmental Pollution - any alteration in the physical, chemical or biological
properties of the environment (air, water and land) which adversely affects its aesthetic
quality and/or beneficial use.
Water Quality Management
A. Water Classification
Depends on the uses of water, namely for domestic water supply, industrial
purposes, irrigation, transportation, habitat for marine life and fish, and recreation
and on how the standards ·may contribute to the environment making the
community more pleasant to live in
Streams are classified according to the bighest beneficial use that can be obtained
from them.
0
0
Water Usage and Classification
(Source: DENR Admini strative Order o. 34 Series 1990, Revised Water Usage and Classification/Water
Quality Criteria Amending Section Nos. 68 and 69, Chapter 3, of the 1978 NPCC Rules and Regulation)
a. Fresh surface waters (rivers, lakes, reservoirs, etc.)
Class AA
Public Water Supply Class I. This class is intended primarily for waters having
watersheds which are uninhibited and otherwise protected and which require
only approved disinfection in order to meet the National Standards for
Drinking Water (NSDW)·ofthe Philippines.
Class A
Public Water Supply Class II. For sources of water supply that requires
complete treatment (coagulation, sedimentation, filtration and disinfection) in
order to meet the NSDW.
Recreational Water Class I. For primary contact recreation such ·as bathing,
Class B
swimming, diving, etc. (particularly-those designated for tourism purposes)
1. Fishery Water for the propagation and growth of fish and other
Class C
aquatic resources 2. Recreational Water Class II (e.g. boating, etc.) Industrial
· Water Supply Class I (For manufacturing processes after treatment).
1. For agriculture, irrigation, livestock watering, etc
'
Class D
2. Industrial Water Supply Class II (e.g. cooling, etc.)
3. Other in-land waters, by their quality belong to this classification
b. Coastal marine waters
Class SA
~
~
Class SB
Class SC
Class SD
I. Waters suitable for the propagation, survival and harvesting of shellfish for
commercial purposes.
2. Tourist zones and national marine parks and reserves established under
Presidenti-al Proclamation o. 1801; existing laws and/or declared as such by
appropriate government agencies.
3. Coral reef parks and reserves designated by law and concerned authorities.
1. Recreational Water Class I (Areas regularly used by the public for bathing,
swimming, diving, etc.)
2. Fishery Water Class II (Commercial and sustenance fishing)
}- Recreational Water Class II (e.g. boati ng, etc.)
/ ~·Fis hery Water Class II (Commercial and sustenance fishing).
3. Marshy and/or mangrove areas declared as fish and wildlife sanctuaries.
1. Industrial Water Supply Class II (e.g. cooling, etc.)
2. Other coastal and marine waters by t]Jeir quality, belong to this
classification
92
P
B
~- ~-sical
_
and Chemical Principles
Environmental Engineering
Characteristics of Wastewater
a
Physical characteristics
1. Color - generally an indication of the age of sewage (e.g. fresh: grayish or
septic: black)
Measurement
0
Visual Comparison Method
Nessler Tubes - color comparison tubes contammg water of different
colors and assigned a color unit ranging from I to 70 where 1 color unit Pt
= Y2 mg/L Co
0
Photoelectric Colorimeters
2. Odor - comes from septic decomposition at organic wastes and is due to the
presence of gases such as
Compound
Amines
Ammonia
Diamines
Hydrogen sulfide
Mercaptans
Organic sulfides
Skatole
ed
Odor
fishy
arnmoniacal
decayed fish
rotten eggs
skunk
rotten cabbage
fecal
Structure
CH3NH2(CH3)3
NHJ
NH2(CH2)4NH2, NH2(CH2)sNH2
H2 S
CH3SH, CH3(CH 2)3 SH
(CH3)2S, CH3SSCH3
CsH 5NHCH 3
Measurement
0
Olfactometer
0
Sensory Method - panels of human subjects are initially exposed to odorfree air and then sampled air which has been diluted with odor-free air to
give the MDTOC. The number of dilutions give TON
MDTOC / TON
where MDTOC = minimum detectable threshold odor concentration and
TO = threshold odor number
TON = vol. of sample air+ vol. of fresh air
vol. of sample air
c
3. Turbidity - the amount of suspended matter in water/wastewater and is
obtained by measuring its light scattering ability. It is also a measure of the
ability of sunlight to pass through water and the ability of water to disperse
different materials disposed into it. A typical clear lake has a turbidity of
about 25 units while muddy water exceeds 100 units.
~-~-----
Meas ement
0
Jackso;;'iurbidimeter - JTU (Jackson Turbidity Unit)
1 unit = 1 mg/L silica in H20
0
S~cchi Disk Depth - depth in which a secchi disk may still be visible to
th~ naked eye when submerged in water.
4. Temperature - lowers the solubility of oxygen in water and increases the rate
at which oxygen-consuming microbes attack organic waste.
5. Total Solids - solid residue when water is evaporated at 103-105°C
93
Physical and Chemical Principles
Environmental Engineering
Phy
b. Chemical characteristics
l. pH - a measure of the acidity or alkalinity of water
2. Calcium and Magnesium Salts - cause hardness in water and the formation of
scales and deposits on pipelines and fittings if used in industry
3. Nitrogen and Phosphorous - basic components of fertilizer, serves as
nutrients for microbial growth in particular algae. Excessive amounts lead to
algae blooms which cause eutrophication or the overabundance in the growth
of algae giving water a pea-soup appearance
4. Trace Metals - refers to heavy metals which are toxic even in small
concentrations.
0
Biomagnification - involves the accumulation of trace metals through
each species of the food chain
0
Mercury - easily converted into the toxic methyl mercury which causes
Minamata disease which is a neurological disease characterized . by
trembling, inability to walk and speak and even serious convulsions that
can lead to death
° Cadmium - responsible for the Itai-itai (ouch-ouch) disease which is an
extremely painful disease that causes disintegration of the bones
0
Silver - causes argyria, the blue-gray discoloration of the skin and
mucous membrane
0
Arsenic - recognized poison, carcinogenic
° Chromium - causes neurological disease
0
Lead - leads to fetal malformation, mental disability, irritability, loss of
appetite and reduction of sex drive
5. Proteins - principal constituents of animal organisms and in large quantities
causes extremely foul odors
6. Carbahydrates - include sugars, starches, cellulose and wood fiber
'
c
ferment
7.
8.
9.
10.
sugar + bacteria
alcohol+ C0 2
Oils, Fats, Greases - prevent natural aeration reducing the use of the stream
for fishing
Surfactants - substances that cause foaming in water
Phenols - cause taste problems in water particularly when the water is
chlorinated
Pesticides and Agricultural Chemicals - have the capacity to biomagnify, and
at certain concentrations, are carcinogenic.
a.
c. Biological characteristics
MPN
Measurement: - lOOml
Uses: Escherichia Coli
where MPN =Most Probable Number
1. Measures of Organic Content
0
0
0
Dissolved Oxygen (DO) - actual quantity of free 0 2 present in water
Theoretical Oxygen Demand (ThOD) - a measure of the amount of 0 2
needed to oxidize completely an organic matter whose chemical formula is
known
Biological Oxygen Demand (BOD) - a measure of the amount of 0 2
needed by microorganism to decompose biodegradable organics at a
specified time (5 days), temperature (20°C) and pH (7)
94
Environmental Engineering
Physical and Chemical Principles
° Chemical Oxygen Demand (COD) - a measure of the amount of 0 2
0
0
needed to oxidize organics using strong oxidizing agents (KMn0 4 or
K1Cr20 7) in acid media
Total Oxygen Demand (TOD) - organics are converted into stable end
products in a Pt-catalyzed combustion chamber and is determined by
monitoring the 0 2 content present in the products
Total Organic Carbon (TOC) - organic matter is oxidized in a hightemperature furnace to convert C to C0 2 .
2. Kinetics of BOD
where L = amount of 0 2 present in H 20 at anytime, t; L0 = amount of 0 2
present in H 20 at t = O; BODt = BOD at anytime; t and k = deoxygenation
constant, time_ ,
For polluted and waste water
For sewage
At different temperatures
k20°c = 0.10/day
k20°c = 0.23/day
kr = k20 8 (T-ZO)
8 = 1.056 (T = 20-30°C)
1.135 (T < 20°C)
1.047 (T > 30°C)
C. Wastewater Treatment Methods
f
0
Wastewater Treatment - defined as the separation of solid and liquid impurities,
suspended or dissolved in the carrier water.
SCHE.\iATIC DIAGRAM OF WASTEWATER
TREATMENT METHODS
PRE TR£A Th1ENT
Comm;o010BiGriodm
Racks or~ Sattns
~ GritChamber
Wastewater
Ph)sical Flocculation
[ Preaeration
}--e-{
PRIMARY TilEA TM ENT
F;oeScreens
Plain Sedimentation
Flotation
Granular Bed
Filtration
Slimming
SECONDARY TREAThtENT
TERTIARY TREAThi ENT
Aoi;vOl<dSl•dgol'nx=~
d
Trickling Filter
Stabiliza1ion Bed
Secondary
Sedimentation
Aeraied Lagoon
DISl1'.'fECTION
N<wraJ;mi;oo
Redox ~ipitation
Coagulation
Chemical Floccubtion
EFFLUENT WASTEWATER
a. Physical treatment methods
1. Screening - treatment used for the removal of coarse and settleable solids by
interception.
Types of Screens
0
Racks or bar screens - composed of parallel bars or rods which maybe
hand cleaned or mechanically cleaned
° Fine screens - wire or cloth mesh or perforated plate
Puroose of Screening
To remove material which would (a) damage equipment, (b) interfere with the
satisfactory operation of a process and (c) cause objectionable shore line
conditions
95
Environmental Engineering
Physical and Chemical Principles
1
2. Comminutors - devices that cut-up solids into smaller and more uniform sizes.
3. Grit Chamber - an enlarged channel where the velocity of wastewater flow is
controlled to allow only the heavier solids to settle out.
4. Skimming - method of removing impurities that float on the surface of the
wastewater.
5. Pre-aeration - introduction of air into a tank in order to remove grease, odor,
improve the treatability of wastewater and promote uniform distribution of
suspended and floating solid and to increase BOD removals.
6. Physical Flocculation - aggregations of finely divided solids to a size large
enough to settle out using agitation or stirring.
7. Equalization Basin - maintain a cons.tant volumetric flow of wastewater from
pretreatment to other downstream operations.
8. Sedimentation Tank - consists of cylindrical or rectangular tanks where
settleable solids are removed by gravity.
'
9. Flotation - removal of finely divided solids and grease by floating them to the
surface.
Steps in Flotation
0
0
0
0
Addition of conditioners
Promoters and activators - form a film and the solids to be floated
Frothers - stabilize air bubbles
Introduction of air bubbles
Direct diffusion
Pressurizing wastewater
Lifting of solid pollutants to surface due to buoyant force provided by air
bubbles.
Skimming of solids which have risen to surface.
b. Chemical treatment methods
1. Neutralization - a chemical treatment whereby either acids or bases are added
to the influent wastewater in order to neutralize any acids or bases present and
thus control pH.
·
2/ Chemical Precipitation - involves the addition of chemicals for the express
/
purpose of improving plant performance and removing specific components
contained in the waste water.
Common Precipitants
o
Lime - Ca (OH) 2
° Ferric chloride - FeCh
0
Soda ash - Na2C03
° Ferric sulfate - Fe2(S04)3
0
Alum - Ali(S0 4)3.14H20
0
H 2S04 and S02
3. Coagulation - an electrochemical process used in the removal of colloidal
matter in wastewater through the addition of coagulating agents which reduce
the electrostatic charges surrounding colloidal matter, thereby allowing
natural Van der Waals forces of attraction to predominate and allowing solids
to cluster.
Common Coagulants
0
Alum - A'2(S0 4)3- 14 H 20
° Copperas - Fe S04·7 H 20
96
Environmental Engineering
Physical and Chemical Principles
4. Chemical Flocculation - a physico-chemical process used in the removal of
finely divided solids, a polyelectrolyte is added to wastewater which can form
bridges that-will join together the solids
5. Disinfection - refers to the destruction of water forms pathogens (bacteria,
viruses, amoebic cysts) for the sole purpose of preventing transmission of
di'sease through water
6. Ozonization - ozone (0 3) comes from the Greek Word "ozein " which means
to smell. It is a very unstable gas and a very powerful oxidant capable of
oxidizing 200 to 300 times more than chlorine. It can reduce complex taste,
odor and color; it has no lasting effect and is quite expensive and found to be
toxic to fishes.
7. Chlorination - addition of Ch and its compounds (Cr or HClO-)
Chlorine when added to wastewater is broken down into:
0
chlorine demand of water - amount of Cl 2 that will oxidize organic matter
0
residual chlorine - amount of Cl2 that will disinfect water.
c. Biological treatment methpds
0
0
Duplication of nature's self-purification process under contained and
controlled conditions
Use microorganisms to reduce the biodegradable organic content of the
wastewater by using them as food for metabolism converting the organics into
harmless stable products.
General Biochemical Reaction
Organic Matter (CHONSP) +cells+ 0 2 --7 simple compounds+ more cells
(soluble/biodegradable)
1. Activated Sludge Process - a continuous re-circulating aerobic biochemical
process that keeps cells in suspended growth
2. Trickling Filters - a fixed bed where wastewater is intermittently discharged
anz:ontacted with biological slimes that have grown in the filter media.
3. Stabilization Ponds - a large shallow lagoon divided by thermal stratification
into an aerobic surface and anaerobic bottom.
4. Aerated Lagoon - stabilization ponds provided with surface aerators.
5. Anaerobic Digestion or Decomposition - generally employed for treatment of
organic sludges and concentrated organic industrial wastes.
Solid Waste Management
Integrated Solid Waste Management (ISWM)
_
= ISWM - the selection and application of suitable techniques, technologies and
management programs to achieve specific waste management objectives
Includes factors like: frequency of collection, type of wastes collected, location of
disposal site and environmental acceptability of disposal system and level of
satisfaction of the customers.
97
Environmental Engineering
Physical and Chemical Principles
Ph
Waste Pre vention and Minimization
Recycling and Reuse
Trans fom1 ati on
Landfill
Solid Waste Management Techniques
0
Route Balancing - process of determining the optimum number of services that
constitute a fair day' s work and dividing the collection task among the crews so that
all have equal loads.
0
Heuristic Routing - process of determining the path or route for the collection vehicle
to follow as it collects waste from each service in a specific area.
g
Air Quality Management
Air Pollution
0
Presence in the atmosphere of substances whose concentration, quality and duration
affect the usefulness of air resources.
,.... A
I.
A. Air Pollutant Classifications
1. Primary Pollutant - emitted by an identifiable source
2. Secondary Pollutant - formed by chemical reactions
3. Criteria Pollutant..:_ likely to exist in all urban areas
4. Non -criteria Pollutant - industry specific
B. Major Air Pollutants
a. C02
0
Main product of fossil fuel combustion; major greenhouse gas when it
displaces 0 2 in the air causes suffocation due to binomia
~b"'
0
Product of incomplete combustion (low temperature) of fossil fuels
0
Reacts with hemoglobin forming carboxyhemoglobin
0
Strong affinity of hemoglobin for CO causes 0 2 to leave the tissue resulting
in anoxicity
c. SOX
0
SOx compounds are acid rain precursors produced when they combine with
water droplets in air to form sulfuric acid, H 2S0 4
S02 + 0 2 -? S01
S01 + H20 -? H28_0 4
d. NOx
0
NOx stands for an indeterminate mixture of nitric oxide, NO, and nitrogen
dioxide, N0 2
0
Nitrogen oxides, NOx. are formed mainly from N 2 and 0 2 during hightemperature combustion of fuel in cars
0
They cause the reddish-brown haze in city air, which contributes to heart and
lung problems and may be carcinogenic
0
Nitrogen oxides are major contributors to the formation of ground level bad
ozone
2.
3.
4.
co
98
5.
=>hilif
a
F
(J
c
F
(l'
o
F
(P
a
F
(Ji
c
F
(J1
Environmental Engineering
Physical and Chemical Principles
e. Tropospheric Ozone
" Major constituent of photochemical smog
" Ozone is formed from the ozone precursors, VOCs, and nitrogen oxides
" Alters vision which prevents the eyes from focusing properly and increases
the calcificat1on of bones resulting in premature aging and depletes body fat
f.
Chlorofluorocarbons, CFCs
" Artificial gases, used as coolants in refrigerators and air conditioners
" The most abundant CFCs are CFC-I I (or CFCl 3) , and CFC-12 (or CF 2C'2)
" Non-toxic, non-flammable, non-biodegradable
" CFCs are not water-soluble, therefore, are nof washed from the atmosphere by
rain
" Stable and can reach the stratosphere
g. Particulates
" PM 10 , PM, Total Suspended Particulates (TSP);
" PM (10) are particles with diameter less than 10 µm
" Cause diverse health effects
" Contribute to urban haze, cause visibility reduction
" Play a key role in the Earth's radioactive budget and global change
,... Air Pollution Control Equipment
1. Settling Chamber - device where particulate removal is by gravity; recommended
for particulate sizes in the range of 50 microns and higher.
2. Cyclone Collector - dirty gas is fed peripherally into the device. Particulate
removal is by centrifugal impaction on the cyclone wall from where it falls to the
bottom; recommended for particulates of 20 to 45 microns in size.
3. Scrubber - uses water to effect particulate separation from the gas stream. It may
also use a counter-current flow of gas in a spray tower; recommended for
particulates of 5 to 20 microns and must have high affinity for water.
4. Filter - separates the particulates from the main stream by direct interception;
filter medium is cloth (canvass or silicon-coated cloth) - 1 to 10 µm or acetate
membrane filters - 0.1 µm
5. Electrostatic Precipitators - most efficient method. Recommended for all sizes of
particulates especially those below I to 10 microns; gas is given an electrical
charge ~ters the device; the gas stream that passes between charged plates
which electrically attract the particulates.
Ohilippine Environmental Laws
An act creating the National Water and Air Pollution Control
" RA 3931
(July 10, 1967)
Commission
0 P.D. 824
Created the Metro Manila Commission
(November 7, I 975)
0
PD 984
Provides policy for pollution control including land pollution
(August 8, I 976)
0
PD 1151
Philippine Environmental Policy
(June 6, l 977)
0
PD 1152
Philippine Environmental Code
(June 6, I 977)
99
Physical and Chemical Principles
Environmental Engineering
Ph ilippine Environmental Laws
PD 1181
Installation· of pollution control device for all motors and
vehicles
D PD 1396
Created the Human Settlement Ministry
Gave N.P.C.C. the power to close industries violating PD 1181;
P LOI. 551
whereas circular no. I prescribe the pollutants emitted by a motor
under PD 984
vehicle as follows:
C0-3.0%
N0 2 - 800 ppm
HC - 350 ppm
Smoke - not more than 20% dense
D LOI 558
Providing for a pollufion control officer for all industries,
factories, agencies, organizations, be it public or private
° Commonwealth An act to punish the dumping into any river or refuse
wastewater or substances of any kind whatsoever that may
Act
bring about the rise of filing in of river beds or cause artificial
alluvial formations
D PD 825
Providing penalty for improper. disposal of garbage and other
(November 7, 1985)
forms of uncleanliness and for other purposes
D PD 856
Code on Sanitation of the Philippines
D PD 600
Prevention and Control of Marine Pollution
D PD 1586
Environmental Impact Assessment Law
D PD 274
Seeks to develop Pasig River and its environs within 3 years
D PD 281
Created Pasig River · Development Council to see that the
program is implemented
D PD 602
Establishes oil pollution operations center in the Philippine
Coast Guard Headquarters
D PD 1067
Water Code of the Philippines; integrates all laws governing the
ownership, appropriation, use, exploitation, development
conservation and protection of the country's water resources:
answers the need based on rational concepts of integrated and
multipurpose management of water resources, and sufficient!)
flexible to adequately meet future developments; contains
~ measures to prevent flood and other calamities caused by abuse
in the use of water
D PD 1160
Empowers barangay officials to arrest violators of laws for the
. protection of the environment
RA 7924
Created the Metro Manila Development Authority, defining its
powers and functions, providing funds thereof and othe:
purposes
D RA 6969
An act to Control Toxic Substances and Hazardous and Nuclea:
Wastes providing penalties for violation thereof
•
D RA 8749
Clean Air Act of the Philippines
RA 9003
Ecological Solid Waste Management Act
D RA 9275
Clean Water Act of the Philippines
0
D
D
100
Physical and Chemical Principles
Environmental Engineering
REVIEW QUESTIONS AND PROBLEMS
1. The process where more harmful substances are produced from less harmful ones
c. Biomagnification
a. Synergism
d. Thermal stratification
b. Eutrophication
Part of the atmosphere where most of photochemical reactions take place.
b. mesosphere
c. ionosphere
d. troposphere
a. stratosphere
3. Organisms that belong to the second trophic level.
b. herbivores
c. carnivores
a. omnivores
~.
It is defined as the role of the organisms in the community
c. trophic level
a. biotic factors
b. biomes
d. detritivores
d. niche
- Process where decomposers return back the nitrogen to· the soils through the remains
and waste of plants and animals.
c. denitrification
a. ammonification
d. ammonolysis
b. nitrogen fixation
6. Involves the accumulation of trace metals through each species of the food chain
c. anaerobic respiration
a. biomagnification
d. eutrophication
b. thermal inversion
- Process of converting nitrogen gas to ammonia is called _ _ _ __
a. ammonification
c. nitrogen fixation
b. denitrification
d. ammonolys.is
These organisms feed on the waste of the ecosystem.
a. omnivores
b~bivores
c. carnivores
d. detritivores
9. Biomes are distinguished or identified by its _ _ _ __
a. dominant plant life
c. type of plants and animals
b. climate
d. geographic location
:.> . Denitrification is carried out when bacteria break down nitrates and release nitrogen
gas. What are these bacteria?
c. rhizobium
a. anaerobic bacteria
b. cyanobacteria
d. aerobic bacteria
Total uptake of chemicals by an organism from food items as well as via mass
transport of disso lved chemicals.
c. bioconcentration ·
a. bioaccumulation
d. all of these
b. biomagnifi cation
The permissible color for domestic water supply in ppm is
a. 5
b. 10
c. 15
d. 20
The resistance of water to the passage oflight through it is a measure of the
a. color
b. turbidity
c. hardness
d. dissolved gases
-
The total solids in water are due to the presence of
a. Suspended and dissolved solids
c. Colloidal and settleable solids
b. Suspended and floating solids
d. Colloidal and bacterial load
101
Physical and Chemical Principles
Environmental Engineering
15. Which of the following is NOT a physical characteristic of wastewater?
a. odor
. b. turbidity
c. color
d. hardne~s
16. Gas responsible for the rotten egg odor of waste water.
a. ammonia
c. mercaptans
b. amines
d. hydrogen sulfide
17. A trace metal which causes the Itai-itai disease is
a. cadmium
b. silver
c. mercury
d. chromium
18. It is a phenomenon that results in the overabundance of algae growth in bodies of
water. It is also the natural process of nutrient enrichment that occurs over time in a
body of water.
c. anaerobic respiration
a. biomagnification
b. thermal inversion
d. eutrophication
19. The red brownish color of water is due to the presence of dissolved impurities of
a. bicarbonate
c. arsenic
b. sulphate
d. iron and manganese
20. The alkalinity of wastewater is due to the presence of the following EXCEPT
a. ammoma
b. dissolved C0 2
c. carbonate
d. bicarbonate
21. Hardness of water is usually expressed as parts per million of _ __ __
a. MgS0 4
b. Na 2 C0 3
c. CaC03
d. CaC!i
22. Which of the following maybe used to measure the assimilative capacity of a stream':'
a. BOD
b. COD
c. ThOD
d. TOC
23. Type of wastewater treatment that employs physical and chemical treatment methods
to remove or reduce a high percentage of suspend solids and toxic materials.
a. Primary Treatment
c. Tertiary Treatment
b. Secondary Treatment
d. Minor Treatment
24. Process whereby coarse matter (suspended or floating) of a certain size can
strained out of flowing water with the aid of bars, fine wires or rocks.
a. screenmg
b. flotation
c. sedimentation
d. flocculation
25. Removal of all settleable particles rendered settleable under the influence of gravi ~
basically the theory of gravity und~he influence of which all particles heavier tha:
water tend to settle down.
a. screening
b. flotation
c. sedimentation
d. flocculation
26. Which of the following is NOT used as adsorbent material?
a. activated charcoal
c. silica gel
b. Fuller's earth
d. water
27. Insufficient washing of sand grains ·in a rapid sand filter causes
c. shrinkage of media
a. air-binding
b. mud balls
d. expansion of media
28. Which of the following is NOT use for the disinfection of water?
a. ozone
c. ultra-violet rays
b. chlorine
d. sulfuric acid
102
Physical and Chemical Principles
Environmental Engineering
29. Most aquatic organisms can survive in a pH range of about _ _ _ __
a. pH= 3 to 7
b. pH = 7 to 11
c. pH= 6 to 9
d. pH = 5 to 8
30. Most commonly used coagulating agent.
a. aluminum sulfate
b. ferric sulfate
c. ferric chloride
d. sulfuric acid
I. Nitrates more than 50 ppm in water leads to a disease called
a. Typhoid
c. Gastroenteritis
b. Mathenoglobenemia
d. Mottled tee
2. The process of killing infective bacteria in water is called
a. coagulation
b. screening
c. sterilization
d. sedimentation
3. The amount of chlorine available in water after the disinfection is called
a. Free chlorine
c. Free available chlorine
b. Residual chlorine
d. Combines available chlorine
:4. What substance in water is removed by Lime Soda Process?
a. Odor and taste
c. Iron and manganese
b. permanent hardness
d. temporary hardness
35. An electrochemical process used in the removal of colloidal matter in wastewater
through reduction of electrostatic charges surrounding the solids.
a. coagulation
b. neutralization
c. flocculation
d. precipitation ·
.J6. These are accumulated solids removed from separation equipment such as settling
tanks and clarifiers.
a. floes
b. suspended solids
c. total dissolved solids
d. sludge
Water treatment that destroys disease-causing bacteria, nuisance bacteria, parasites
and other organisms and removes soluble iron, manganese and hydrogen sulfide
-------..
from water.
a. disinfection
b. chlorination
c. flocculation
d. coagulation
A neurological disease characterized by trembling, inability to walk and speak and
even serious convulsions that can lead to death due to ingestion of mercury
a. scurvy
b. minimata
' c. itai-itai
d. argyria
'9. Type of wastewater treatment that employs biological methods to remove fine
suspended, colloidal and dissolved organics by biochemical oxidation.
c. Tertiary Treatment
a. Primary Treatment
b. Secondary Treatment
d. Minor Treatment
0. A wastewater with a BOD/COD = 1 indi.cates that _ __ _
a. chemical treatment is required
b. biological treatment is most practical
c. the wastewater is highly polluted
d. does not indicate anything
~I.
A continuous re-circulating aerobic biochemical process that keeps cells m
suspended growth
a. activated sludge process
c. stabilization ponds
b. trickling filters
d. aerated lagoon
103
F
Physical and Chemical Principles
Environmental Engineering
5
42. When a sample of water is added to a medium of agar and incubated at 37°C for 24
hours, colonies of bacteria formed are countered. This test is called
a. Total Count Test
c. Confirmative Test
b. Presumptive Test
d. Completed Test
'
43. Aeration
of water is done to remove
a. suspended impurities
b. floating impurities
c. dissolved salts
d. dissolved gases
44. Legislation that presents the revised water usage and classification.
a. DENR Administrative Order o. 34
b. Philippine Clean Water Act of2004
c. Water Code of the Philippines
d. Republic Act 9003
c· ·
45. Clas~ of water intended for prirna~ntact recreation such as bathing, swimming,
skin diving, etc.
a. Class AA
b. lass A
c. Class B
d. Class C
46. What is the atmospheri condition when the lapse rate is > 10°C/km?
a. adiabatic
b. subadiabatic
/
·
c. superadiabatic
d. none of these
4 7. A global treaty that aims to regulate emissions of greenhouse gases.
c. Kyoto Protocol
a. Stockholm Convention
b. Montreal Protocol
d. none of these
48. This provides the blue print for action towards sustainable development
a. Earth Summit
c. Montreal Draft
b. Agenda 21
d. POPs Convention
49. Generic term used to describe the particulate matter carried in the effluent gases from
furnaces burning foss il fuels
a. PM 10
b. TSP
c. fly ash
d. ESP
50. These reddish p{own oxides in concentrated form may produce an abnormal
accumulation oq fluids in the lungs.
b. SOx
C.
Ox
a. CO,
d. TSP
51 . These are closed compartments that use gravitational force to extract dust and mist
and typically used only for larger particles.
c. cyclone device
a. electrostatic precipitator
b. settling chamber
d. wet collectors
52. A global treaty that aims to diminish and eventually phase out chlorofluorocarbons.
c. Kyoto Protocol
a. Stockholm Convention
d. none of these
b. Montreal Protocol
53 . It is a very unstable gas used for disinfection, a very powerful oxidant capable of
oxidizing 200 to 300 times more than chlorine and can reduce complex taste, odor
and color.
c. ozone
a. hypochlorite
b. hydrogen peroxide
d. fluorine
104
5
5
5
5
5
6
6
6
Physical and Chemical Principles
Environmental Engineering
54. A phenomenon where a cold layer of air becomes trapped by a layer of warmer air
above due to a lack of wind c.irculation or the .presence of certain topographical
features , such as mountains, resulting to air pollution being trapped in the lower,
cooler layers of the troposphere.
a. global warming
c. greenhouse effect
d. anaerobic respiration
b: thermal inversion
55. It is described as the cloud of air pollution trapped by thermal inversion.
a. CFC
b. smog
c. NOx
d. S0 2
56. A global treaty that aims to protect human health and the environment from
persistent organic pollutants.
c. Kyoto Protocol°
a. Stockholm Convention
d. none of these
b. Montreal Protocol
57. PAN is a powerful lachrymator or tear producer formed from unburned
bydrocarbons, aldehydes, nitrogen oxides and oxygen. PAN_stands for _ _ _ __
a. peroxyacetyl nitrate
c. peroxyamyl nitrate
b. peroxyallyl nitrate
./
d. peroxyalkyl nitrate
58. Component of CFC's that causes ~~/ttuction of 100,000 molecules of ozone.
a. carbon
b. chlorii . ,
c. fluorine
d. hydrogen
59. It is used as bonding agents in quilding and furniture construction which may cause
drowsiness, nausea and headachb when exposed to low level concentration.
a. formaldehyde
b. radoh
c. PAN
d. CO
~rer percolates through any permeable material. It can
contains either dissolved or_ s.~nded material, or usually both, anoxic, acidic, rich
in organic acid groups, sulfate ions and with high concentrations of common metal
ions especially iron.
a. sludge
b. leachate
c. bottom ash
d. all of these
60. The liquid produced when
61. Recyclable material labeled as no . 3
a. PET
b. PS -
c. PVC
d. HDPE
62. It is defined as the controlled' decomposition of organic materials, such as leaves,
grass, and food scraps.
a. composting
b. putrefaction
c. incineration
d. recycling
63. Type of recycling that involves recovery of chemicals or energy from post consumer
waste materials ..
a. Primary
b. Secondary
c. Tertiary
d. Quaternary
64. Ecological Solid Waste management Act of 2000 is otherwise known as
a. RA 6969
b. RA 8749
c. RA 9003
d. RA 9275
65. Which of the following is NOT classified as heavy industry in the list of
environmentally critical projects?
c. smelting plants
a. iron and steel industry
d. forestry projects
b. non-ferrous metal industry
105
Environmental Engineering
Physical and Chemical Principles
66. Calculate the theoretical oxygen demand (ThOD) of 150 ppm glucose.
a. 104 ppm
b. 116 ppm
c. _137 ppm
d. 160 ppm
67. If the three-day BOP (BOD3) of a raw sewage is 55 ppm (k
ultimate BOD?
a. 68 ppm
b. 96 ppm
c. 107 ppm
=
0.55/day), what is the
d. 123 ppm
68. Determine the theoretical oxygen demand of 100 ppm of glutamic acid (C5H;0 4N)
according the following reactions:
C5Hg0 4N + 4.5 0 2 -+,. 5C02 + 3H20 + NH 3
NH3 + 202--+ N03-+ H+ + H20
a. 44 ppm
b. 98 ppm
c. 130 ppm
d. 141 ppm
69. The pH of a water sample was found to be 7.5. The bicarbonate was measured to be
2.1 x 10-3 M. Assuming that the sample was isolated from the atmosphere, calculate
the total carbonate is pK. 1 and pKa2 are equal to 6.3 and 10.33 , respectively.
a.2.2x10-3 M
b.2.4x10-3 M
c.2.6.x10-3 M
d.2. 8x l0- 3 M
70. A water sample was analyzed to contain 150 mg-L- 1 co 3- 2 and 100 mg-L- 1 HC0 3- '
at a pH of 8.00 at 25°C. Approximate its total alkalinity in terms of mg-L- 1 CaC03 •
a. 166 ppm
b. 332 ppm
c. 489 ppm
d. 664 ppm
106