THE
EQUIL18R\
I
SILVER NITRITE
UM
vvth S LVER
SILVER and WITR\C OX DE
N ITRATE, METALLIC
the
andc
FREE ENE-RqY of SOME
N IT-ROqEN
COM POUNDS
A THES15 PRESENTED at1 the MVASSACHUSETTS
N7ST1TUTE o#f TECHNOLOqY
o- BACHEL3O1
ADAMS,
ihe
of SCIENCE
L
by E LLOT
COURSE IM, 19Os,
DIRECTION
MAY
of
for the OEqREE
Q.NC09
P R E PRE; unde•r
PROP. GQI LBERT N. LEN\IS.
25, t909O
An Eqliibrium oU0Silver
Energy Val ues.
NitAite and Somýe
Stefan von Nierenntowshi and Johann Yon.
In 1897
Roszkowski whi'e making
Licpc tilhat the solubility of Siver
of Aniiine,
Nk trite
in
! a ter
made by sat'
-irLpg
fi lt
oil
anci
stuidy of ihe Di~zot zation
when the solattion was
was IeS
wVter at 50°oC wt7, silv
e e.xCess
after C~ioohn
nitrrte
L'O
to
roo
Vý-,O
than rvwher, the solucoo was saturt
by
and lerng off the
S!aP; rt o
IOnl-cIfLiA
m temperature , a very
ve& residve at r~e
wnn4isso
surprising result in viei
siever
nitrite with
of the -rapd \nrerase in solubility
n4eteomoeratl3r•rise.in.
r
in 1905 A\ex. Naumann ainc Adolf
iv'~II rnakin9
an inesato
of the i rnUence 0 isilv9jr
nitrate on the solubility of sflver nitritefound that
the discrepancy tound by N'iernento wski
an
Rosz
kow
0
0 sk* was The result of a r-action by which
Slvy
nitrate,
nitritoxiae ana metallhc sil\er
were
An Equhilbrium of ilver N tritie and SomeFree Energy VaLLes.
stoi-cal
(continLeci)-.-
+orme
from si11ver nitnite, The zaveizr investigators
h3ving
appayrentiy +Titite6
for the- concentation of
nitriite, which had .been diminished by the increase
in Silv~ ion concentration
resulting from The siYver
nitr ate present in tLhe Solution.
to obtain
constant
They we4e unab\e
valuies for I-he solubi\ity prodt
o: silver nitrite an& assumed that the theory of
E ectrolytic DUssoci
ation
was at fault.
The same year R.Abegg and. Hans Pick
Showe-d th t
this resuit was cieto thpi Prroneous
i vr?
assumption tha-t the dceree oi dissoci ation o± So
nitr~iti
as the sme as that of silver nitrate ,an&
si
grze of dissociation foun&
Yalu s of the cLd
by zelctrical mr-eho s.+ound
3most satis$actory
a
'onstancy
of t1he sol b•i;ty produc of sil ver
nf rite.
__
1An
brim of Silver Nitrate and Some Free Energy Values.
Equi 1i
Historical
in 190G Alegg and Pick m1ade an inves-ig -tionof
thz
E lctro-aHinity of nhe Anions, EZ.-
The Nitrite-
ion and Wts Equilibrium with Nitrate anck NO.
The experimeYnta\ worklS/nclI.dec a. cLdterrination
of lhe e-qiibrvum
constantrs
at 55oC fbor he raaction-.
Ag'+ NO', + A
with a study1
of the- Formation
of Complex Ions
NliAite and M.ercLLr• Nitrite.
cal cIul tions der made
moU•;v
.)- ------ I
- o,
in addition
a nd of ekctro -
of free enxerg
forces.
--
---
=
An Equilbrium of Silver Nitrite and Some Free Energy
va·lues.
(contiinue d) . -
They
found for the constan :LKý jx EN03'JxPW
Nhere Pto rý
c
0tmosph .re s
the prs
anct
Conc ntr ati ons
pe r ite r,
of
___~~
in
SilVPT and n-tra
1e
in two dCterminations
_
xiae in
P
nitLi
LAgJ'I*NO3'] are the ion)i c
~jtl c~q ui ii Dri l)rTI
O. 81 x lo-'
sure o
and
at
tempeature I
th9 va) LLues : -
O. 89 x 10
___
rnolS
An Equili bri um of Silver Nitrite andSome Free Ern7ry Va lies.
PLtr pose : The purpose of this thesis is to coyroborate the
resuLts
obtaijned
by Abegg and Pick with regard to the
•£kP rzaction Ag'+ NO3' +Ag + NO
2 ~YO·
by
study in g the equilibyvium a"t a
hihrh,
teamperatu.e Than that at
ciLfferevt,an&
which Thpnir
ires
mcasc
Nltre macle and to maue such caaulationis oýf free
enrgy
oC
ompOTLYndS ci
oxCygPen And hydroven
-thus obta•ined
s
nitroi nI
vA/Ih
c-an be mnacl
oxygen and
tron
Iv;
Lhe data
and pr~eviosly knowny free energ
values.
An Equilibvium oi Silver Nitrite andSomKi Free Energy V\kLtes.
E xperimental Ivork iwere rmave
Two -ftes cketerminations ,,of th• prssres andC
lnbriv
councnT rations
pre irn;nary Yrkl
at ioo0 C,•
i
ha 1-n0orna)
LuS i n
Soithion, and a fina\ one In NhiCh normal SiyjeY
was employed.
The horms of apparatus
two dietrni n ations, as wel as That
and Pick
shown
Gae
Ltsaz
LLSZct by Abeg
in LhF sklc hes.
(.·B
\-.-i
F
A pparatu.s
Ltsect by
Abe~g
C
n
3a~Liofs~.
E
ancL
Apparatus Lsec in pre;minary
d9½trrin ation.
The. apparatus we.re p\aced
47•"x
in a steam bath made of an iron pipe
N(dia), vih &screw capat
p he \ower en&,lagged" wiA magnesia
asbestos, and ciosec- al the
t ipperend by d co(k witI
~--~--
andSome Free Energy
An Equ\i brnium o Sitver NiTitir
vaiLLes.
Eperimental work': The
holes ýor the mnanometer tLAe and for a condenser.
heating was dolne with a Thirre)l b arner.
Haterials: -
Silver nritrite Was macLe b precipitAtion from silver ntrate and
e in imounts as nearly equivalenit aS possible.
o'tassiim niTriT
The potassiam nit•Zre fornme~, ano
Zhe excess ot onegant or
Th'e oZhr
by decantation
.bere r0moYeah by ashirg
al neady
ate as
silver w/a proou'ed by nieatI5 sa
a
5inca:7e No proaced
:~ne
Of
QohlttionS
Centrations
y hI
3at!
-''ria~p^
reactio
,si
v
Vd~
fii-rllr
nri&rCZ
of0 sie
0.5
CrVaiticabl~
of - vei
o& the
+noont
11ae anna adc6isg 1be exact amoi-nl ~7e
concen~a
reLto
eicae
the
COm~s~~-6~.
c
rnO^noal
con-
i.3
8,n
as nearly as Qossi be The
Solutions oiy
spe'nsion
toer jor several says on the bteam table.
h
oi siier nitriae in
o0
'v"Aer
'O0C as
is possib.
ossUp
hMealditi
Conv e-rs ion
/viCh
"~
L r ~s "67
d tP 3i
qrg
salt for 100 gr•,ms
'o-rNdat
An Equi\ibrium osSilver Nitrite andSome Fee Ener•
1
cpevrimental V~or k: -
~M atc
rials (r
cont
r ie..)
Niitric oeiie
aS proyue
+or copper vire and
13y
pdS~d~jp ShYough
jn-She gugfini~av,
.20
in
d
sp.Cr. nricai
jadd--time
de~r~Yn;na2~;r;n,
9nrato
tih Kipp typ
an
prie
No n-h
;ric oxidio 4as zsi
An Equilbr;~um of Si\ver Nitite and Some Free Energy Values.
Experimental work .-
Preliminary determination,
For the prehnminary dgterminatioyn a- suspension of
silver nitrite and rnetalic si~ver in exactly half-normal
silver nitrate solution was employeL.
The pressu~re at equi~tbriuvm Was measured but on
aczo Ln-t of the d'i\Iten9ss of the sotLutions, the
hihpr~ssL1ire
genrate-t
which hcad been 1
a
'ct the \arge
gSs Space
h6ftsoltion, the correctionfor
above [he
the change_ in concentration of týhe solution
as to mnahe '"t imoossiQbe
the accuracy desired.
6t
~rin the
to
s0
btaifn rtes jts Co
The- corrrectLn {fr the air-
apparaltus atthke beinninf
was ajso 4ncO-Ttifn.
wVaVS
of the experiment
10.
An Equilibrium of Silver Nitrite andcSornmFreeEnergy VadLLes.
Experimental work (ContinLued):Final deitermination,
was Jil\ed with a suspefnsion
The apparat
Sil v
ni triteo and metallic, si\ver in approximately
normal silver n'tritiý SOuLtionY
being takqn for analysis.
by nLtri~
was dLs place(
samples of Theliquc•
The air in the apparatus
oxide before sealing.
The apparatvu was heated for three houYvs
bath.
in a. stam
The pressure remain&ed practically constant
during
the last hour.
The nitrite ir The sanrples was dttertminevd by titration
with ) MnO4 solution and the silvercontenot
by titrztion
KSC W.
After
cooling, the capilary manometer tube, D,
was removeCd from ]neI apparatLus and the weights of
)
ercu vy req
6 red to f-il h?
1 volume occupied by 1h e ga.s
i.n the manometer initia1ly and at equilibrium, measurecd.
F
I .
An Equl\•ibrium oi Silver Nitrite and 5ome Free Energy Values.
Experimental work (concludecd),
Finai determination,
Data Obtainedt,1.0.93
Initia~iAgNOs concentration of the solutio1n.
i.e., the volumt
4-- Gg-3 wt. molaW.
of solution containing 1000
i. 093
rrams of w4ater contains
+.-aýc mot. AgNOa.
Ratio oi ga s space to in'tai vowime oi liquid, estimated,,
In tia
pres;sLre- in mlanoyneeter, re'tucect,
in tiai
tekmperaltre of manoMeFter, approwimateiy,
Barometric pressure at eq uilibrium, recducect,
Boi1ng point of wadter at this
lempera LLare
pres s ure
of manometer R•I eqii ibriJfm
Weight of mercury coTre spondin
ir\ \ ar
vo•lume of gas in
0.10
763.
m2m
2000.
7G 2. 8""
loo. 10oc
21.6 c.
to the
hhe mnan omelea1r
.7 4 grams.
mercur y correspondflng
volLume o0 gas in Ihe manometer at equilibrium.
0. 713 grams.
12.
An Equi br \um of Silver Nitrite and Some Free Energy Values.
Ca CLlations.
The part-al pressure of NO at equilibrirn:The initia
1.00o
pressure in the manomeiter was 763.3"m
The ratio oi the pressaures is the
atmospheres.
inverse rfatio o0 the voiuLMes =
7
.7 Hence the- total
pressare at equiclibriLam Nvas L.o0x o. 7 -- 9-50 Atmosph~rzs.
The. Vapor prZSsLre
lmperatture
o0
pur!e .atý!r
,NaS 7G2.8 mm
i.004
at the equi.ibrium
aLmosph~res.
The iapor press Lre o" vi•at~• romrn heso•Luion 0.S7atmosphere.
The partia i p ress Ltr
at
o
nitric oxic e in the appayatus
equibri m is :
PNO= P-
o=.o 9.50-0. 97= 8.53
PNo =
100.10
853 atmosphere s.
J3.
vEnegy Values.
An £Equi;brium o0 Si\ver Nitri'tand Some free
:
LL)
(conlinu
The change in AS N03 concentration,Cte to gas spacP :The initia\ concientration of AgN03 was
-If&* wt. molal.
The initi•al pressure 'in theas space
I.o05 atmospherts.
The prissu re a eqiei bria~m in the gas space
9.50 dtmospereS.
The Specfic vio\ume of watur at
1.002.
oi vVater at 100oo
vo\uIrame
The specific
1.04 3
The
t'atio of gas space to initia\ volum oliisuid
in
1f Vo isthveinital vo~lum
itia
v
m,
of
0.10
t;ters
liqlld, 0.10o is he
1.04 Vo the volume
l."
the gas votlume.
o~ I quid at equil;briLim and O.
The nunber oi moros of NO originally presznt vas:-
No
=
PV
T
0. O 0 4 2tVo
-7i
moi.
The. amount of NO present a.t •qulibr;a
N,-RT
-
o.821 x 373
Nv,-iNa 0.013$Vo mto.
O 01 67 Vo
of NO
and
'Nas:mol.
therefore of AgN03
Was formdid by thI reaction in approximatdly 1OOOV gr. HzO.
C
1. O1
1.093
-~Te~1111----------
~~~
1004
CWASWOIZ
100.0
4
____,
~
_-
-
111111~-~31~
1
II~---~I~-·-·--I---
1. 10
-~___·_~lr~
t4.
rAn
Eqcuiiibriu~m o Silver Nitrite anct Some-Fre EneTry ilu es.
Calcfiations CcontinULed)
The reduLction oc Pwo to 250C:The partial pressure of nitric oxide atequilibrium was
8.53atmosp*hirs.
The termperatu.re of equilibriLmt.
100.10°0.
Cw= 1.
I
2Ag~ Oz = AnG
0, +Ag+NO
Sat
'h A^%No
Ps 21 PIt.,+ 0.2 Il
2
()-
;G
where Pwo isThe pressure, in atmospheres, oi nitric oxide in
equiibrium
wi'tb
a
t. weight mola\ Solution of• sivr nitrate
siivqr and soclid silver nitrite.
sol\i
iQ
is the heat absorbed
qwhen ti'o
moos o0 ASNo 2 rTact to
omrnm
•it
o.
MLth
I mol of Sitve nitra•e
s\\ve. n•trite,
I mrno
i~
olait soluionr,satira~d
oi solid sv~.er did I moi o0 nitric
oxict?, and is as
S~rSncd ineppndfnt oi The t~e.perat-ore.
irl the absence oi rnor
I
aCccUrate innorsinaion The
h-at
ol formton÷ o+in
P. lver
Ii
,foai
Sol•ulion,
~
_
_
_ ~
satrahd
'
~
~
ni\ta
LthAQ
~
~ _
,
_
,is
amnct
_ ~___ _
o
_ _ _ _
15
An Eqc
bric um e of
'Silv
7rgy
~t
Nctrite -an•oAmnc
Vaiues.
Calcuilationss (cOnt-;Inec :(condaid) : -
The reduction of PVo to 2,5
$ = Q for Th• reaction.
2AgN(Qz= Ag-' +
a' + A+NR
Q = + 2-0 700. cal.
PNO2
ioS G2.5
log PNo
+0..21
100. 1
= iog 8.53+0.21
Q = + 2.0 700 ca .
20 oo.x
732. -2 89.)
Sx 20700(o.oo2s68-
0.oo 33Zs5)
= 0.93 1 +0.2188x20700 (-o0.000 675)=
= 0.93 1- 3.05 7= 7. 874
~L~,~~IIC·CI
~
~~
P.o= 7.48x 10-3
An Equilibrium of Silver Nitrite and Some Free Ene~gy Va luees.
Ca culations (continuxed) :
The value oO K
at 2,50Cfor Che reaction:-
No
2 AgO• = Ag'+ NOa +
K-=
4Ag* i
Lj03' x PNo ýsee pge 4).
The pressuLre of niLri
lith a
1.10
oxid e
in eqZtii briUm ~a
25
k
AQ N 33 Solution and solid sil vir
lt. nor•ai
and silver nitrate
atmospheres.
Sx 10-
The equivalent condýctadnce of Si lver nitrate a`t Inin'te
diilLton is .5.5,7 + GO.8 = 116.5 = AA NOJ
The eqCivýient condaLctan ce
is
water.
G.3,
at IS0.
1.1 nforma\ SohILion at
oA
its viscos\ty
1.13 tims th-at oi purt
epree o- dissocltion
Th~
is thyhe-efore a-ppa matey
n6.
5.
S0. G43
Theeoncntra ti on o s ii •, ana nilrate ions 1'romn Th si) vr
ni-I
tfaze Is thcrforio
of silver ion from the silvIo.r
Heznce
12s
=
The concetratio-n
1. I x 0.643 = 0.707,
- .1
n trite
is negH1ible.
.
0.707 x7.48x10 - = 3.74x1t
4A 25 = 3.74 x I0j
I -I3L II
---
~
I,
_
_
_
_
_
17.
An Equ libriam o ilcver Nitrite and Some Free Energy Vai uLe s.
it
Cal cuLations (continueed):
K .s from AbeSS and P1ckls
PN
and
0
CANo
The partial pressure e-f NO at 55t
R
4.28 atmiospheres
wx
:i
,2a
\n eqv•ulilbri ;Twih ASNosolution ofConentration,
Soji~ s;~~Jer
nitr'i"le
0. 17 8
molat
andT silver.
The pressure of NO redLeed to 2-50C (see paze 14) "s.
fu nd as folows: lo Pzs= log Pss+o.2188x20700x(+
-)
= og 4.2.8 + 0.2188x 20 700 x (0.0o 3048 -o.oo 335,5)
0=
. 3 1+ .218 x 20O700ox-.00 0307)=
0 ,3
P
1 - 1.390
,
The equi valent condLctance at
so lution is
The d.e
9-3
0
o, dissoci ation cse page 6) is approximai•ily:-
And k=20. 140
\I6.5z
0. 7835.
--~
0. 140.
ion is
x 0. 174 = 3.+2 x 10 "3
= 3 42 x lO- 3
k<
~-~-c----
0. 174
0. i 8 mola\ AtNO3
k..
The con cerntration o silIvr ion a nd of nltr-ik
~lsllbll
=
90,0, its vis osLty 1.01 x that o{pure wavter.
30,0 x 1. O 1G
25
o
_
I
-
.
-
_-
An Eqix\ibri'm of Siuver Nitrite an d Some Free Enerany ~lues.
Cal
ecd) :
ations (Contni
~ies Yor KSs.
va
,s
023 from Abeý and Pick
=-- ' NO+
2I••
i
og ts5
Kg
+ NO-2O 700.ct.
O.
0-2188
20 700x
i5,
y(
s
= log 1~ - 1.390
and Pick obtained for k-ss in tvo Letrmi naiont
AbeSg
thQ YzviJLtus
0. 8
x 10-'
an d
O. 8ýx
The correspondin
vLLes oiS Ji s .re
ya
Kz2y
=
lo K5, - ). 30
fOLLnd1
G,) --o1 0.08 - 1.39O = 8. SO-s-1. 3S0- 7 1519
(b) - lo1g .o 8 - S1.39
-I~--·lll-
__
.949-1.390o
j
aS fo:lows .-
R:-_s(= 3.30 x 10
79
. 5=7
_____··___lll~·C- -
~.~iS_5ei·-r-^--=i~~-~~--~-~--.-
I9.
An Eqlilibrium 4 Silver Nitrite and Some FreeEnergy Values.
Calculations (continued):
Sammary of values of K•s:-
From Abl•gý
and Pick's Vdilu
o4 P,and C,
55
From AbegS and Picks Values o0
h4s
3.4-2. x 10"3.3 0 x 10-
tvvo determxinations
Mean of the above
3.4"5 x 10-'
From the experimental work of this thesis
3. 74 A 1i0- 3
Mean of tLh e last tvvo
__·___II__~
B
20.
An Equi Ii bri um of Silver Nitrite and Some Free Energy VjlLLes.
Calcu lations, ('cOnti nuie)
Z.igN
(T)
:-
a= AgS+ NOS' +
+ NO
Des irecP i.F 2s for normal conc-ntrqt
ILitriLe
ion,
nitric oxide a
K
=
3.6 x
"
o10
ions of si) ver and
atmospheric prlssurle a.nd solid.
silver n;tr-ite and rnmetallc s;lver.
The val Le, 3.G x 0 , for 8 = EigAS1x ENo0']x Pj , (see page 4)
is the mea n of th e vatL.es founct by A begý and PlcVý dni
i ven
CL
that
ear-er rin
this
tkesis. (see page 19)
in free enrgy from
The change
solid sliver nitrite ~to
mola 5ailvver ancd rnitrite Ion, sohid si\vey and nAtrc
mos
0tphe'ri
S-
prssuYre;all aa2"I~~
RT
nK
+
330. cal.
-45
Tx
3.6 x10= -5
F2a =
---
4111111111~---·--
axid.e at
1
________~_
(-2.
+ 3 3 30.cai.
__
~~__ ~~__~~
I~
21.
An EqLui\ibrium o• Silver Nitri t
and Some Free Energy V'altes.
Ca \lCtlationS (contin Led) T.
Age n
.
L 2s= 2.1x10 -4
Ag + NO2'
The free energy cha nre from Solic' S\ve~r nmiriite to
mol
a
ver)on
nol al -SI·erTA~ina moial nli tLi L ion .3:-
-4=.57 T
= - RT n L
SF
S- 4.7 2-98 x (-3. G78)
~r~C
1-~--
-------
~-·I-------
~-~----~------
I---·--
-
----
-4
2. I ox10
+ 5 0 10. cal.
a
-
°
--
Fs= -'+5 0 0. cal.
---
~.~.,,~~..,...,~~,~
.~.~. ....~~
22.
n Equ'iibrium or Silver Nitrie and.Some Free Energy Val Les
SCa \culations Lco ntinned SHB= +21 GO O.cal.
PNO
(s~e ae
IiOOCAbS
=I 2.4
8x 10V
t equsilre bri
At equiibriumn
K
vhen
P= 1 tor all subsItances.
SFz
A Ho t RT
- 2-1 Go0.
OO
C Abs. log
14.40
•')
At
2. G;oc
7
A F =2
T
-4,5 ý,97K -
T
,3_ 21•
= i'og 0.00o24 = 7.33,95 -2.605
-.. 4 g
p so= H!.81-14.40-=
•0'
' r2_
·t57~(·-fl9
j
T1-= -2A49
4.571og8--
8.30
i ,oo= -2. 5
= .80
2.500
C Abs.
+
7iT=
RT&nK+IT
At 2000°CAbs. 1oS8 iog 0.o gs= 8.\85= -.i85
7
LT z
K - CpT&T-
P2A- KT-i £¢.
At)500o
• .Soo'C Abs= 45.5 x -0 3
.20oooAba
s 15.3x 10,
= 21
RT, & K-+T=
Ho= nH8 =s- H
d,.= O. p= O.
g
a Cp = O.
log K= top 0.0455=8.658-.-L342
Zs5 oo = G.14-
8.G+
=
- 2.50
4.5371 o
- P. 14
I
2zoo= -
2.50
I
mean; -2.50
Oi6oo+ IT; 21 Goo+ 1-2.5o298= 21 600-745-20850.
'i
ib
·
s
6 Fes =+ 20 850 cal.
-ISIIIIIIIIIILI
~_
_~~~~~~~~~~~___
23.
An Eqtuihibrium ofSiiver Nitnte and Some Free Energy Vaclues.
:
Tin.ecd
Ca\cuýatioas (con
2NO+H-+N0O+H
(-X)
6 F2s
(Y*)
as
is5given
H N0 2 . =
+NOz'
The change in free
2
.O
+
.2
3 HN0o..
400 cat.
K
A
2s
= + 2 400.cal.
,5:0.0005
enerpy in 8 oin 8 from
molal nitrous
acid to moial hydro8 emn ion an d notla I nitri t ion it
256C is: -
- -4.57T iog 0.000a -4.57x 2 8 x(- 3.301)
= + 4 500.
A Fzs= + 4 500.cal.
:·
`j
24.
An Equil-bri um o1 Silver Nitrite and Some Free Energy /alu.es.
Cal cLlations LcontinuecL:;
Ca). H 2+a-O- HO
H I"atmnosphere), H' "/,10 0 A-tmos phere)
Two Faradays of e\ectricity wi*1
The chhane
&at
In re energQ
8
E = t 1. 2 7 voits.
pass pqr drni oi the- rea.ction.
from h y cdroen
and ox~ygn,
tmospheric pre.ssuLre ,to ,Iater, all at 251C, i s. -
6F2= -
:- = -1.217 x 2x.96580 + 4. 18
= - 5G
70O.
A F5 = -56 170. ca].
-·'---
-
~-·
-31
__11~.
,
.~...._..~~ ~,~,~~
... ~.....
25.
An Eq aii bri m of Silv . Ni tri~t anc some Free Energy Va)ues.
Calculations ccontlinuLe:)
~r~·
+ H2
~3'
Ag, Ag' n/ , N.E.
E = -
9n,eveh)
HFoatmosph
, N.E.
E
=
51
volt.
+0. 2 83 ott
Frosm which:
Ag, AS
Ho
/, hi
t,,osphere
,il/
On e Paraday of eiectricity
Hence the change
Silver anc modi
E = - 0. 798 -1olt.
witl tlowsyer unit oia rvactionM).
in free energy in
hydro en, ion, to
gaoinc 4rom
mooai
sitveur ion a~nt
hydrogen at atmosphsric pressure, allat 25",
a
F2s
-
E
E,
=
18 4120,
A Faz
- ~C
~ - - -
---
-
,
is:-
~
~,..,
= T 18
20 ca .
_~.... ~...,,,~_~,._~. ....~.
26.
brium ol 53i1er Nitrite and SomeFreeEnery v'alues.
An Eq ui hi
Calculations (continuec):
Summary of
free
,Ir Zg=
()
:-
A +N03o'+As+ NO
F2;.5= +± 3 330. cal.
Ag + N
Ag NO
i2 Oi+&TL
010
ct at
enfergfY
o0 o. ca.
O
20 850. cal.
:z) 2 NO6 +IH'+ NO' +HzO =3 HNO2+
SH N 02. = H 'NO.
qI) 2
-= A +& Hz,
+ H'
iR
Rz
+ 1FL+
fq.YT
2
4 00.cal.
aF-= +
4
500. ca\.
4Fas= -
+ 21`3O = HO0
}I)
Ct~Ll)
'
SF~e•= +
5 6 170. cal.
sF2 = +- 8
4 20. cal.
A
IJ
7Z + N.2
-
11111
1
~
_~~___
~_~__~~~~_~__~______r~-i~
a·
·
27.
An Equ\-brvium of 3\1ver Nitrte a.nd Some FreeEner y
.
i ~e
Calcutlations (contin~edj
Thle relations of eguations
to(i
D-9
na
d~0.
S ubstan ce
I7St ~9.
AS-NQ0
I
-2
NOst
I
-
-
j
-
I
A-I
-1 +2
NO2'
+
+1
tii
+1 +
+
H*
HO0
±1
HNo,
++
Hence to derive (yIE)
and ()
(ZIID
-I
L·
~
---
_
_~~
-2+1 +i
2
+2
take. eq-atior,s
+3 -G +1 +2 +6 +2
+
~2-
+2
-43
+1 +
times.
tune s.
~__~~~__
An EqaiiDbrinm of
Silver Nitr~ie ana Some rerEnergy Vaiiues.
Cal culations (continued) : -
UKn+)
6
+±+±±
IO,2= H'+ NO.'
Fzs =
S+
=+
3 x 63 333)
9 990.
S-Gx ((+ 5010.)
S+
oGO.
-30
5
l x i-2.0 85o)
+ 20 850.
S+ 2 x (- 2 4oo.)= + 4 8O0.
27 O00.
+ Gx (+4 4- 5O.)-+
+2x
2 (-5
E
-
170. j
+iH7900.
atros pht~c
·rf~l
I-
340.
+ 55 2 o.
A(4i 8 422 0o.
trom hydro
12
- 142 400.
oom-c4 an500.
C ~.oxy
al
n, nitro en, aand
press L re
o mnoiai
nydrogo~n ios
~mcli~i
__
__~__~~~~___~~__~____
An EquihL•briain of 3iiuvetr Nitrite and Some Frenerny ia'es.
Cal cýuations (con clcLed.:) (IK)
.t4H
+
Nz
z
+ x (-3
:
-2x (+
a
+ixT+20
3X30.)5 0(O.)
=
850.): + 20 850
2 400.
170.)=7
- x L- 5
4.
x
- 56 170.
t+ !%
-+-
Is4-20.
R4(\(W
.
L
BeCr--F
I
·I·--
--
L
10 020.
-
4 500.)= + 9 000.
+2x (<I
r. +\
3330
+ 2 400.)=
-a +\4x
z.
+Oz = HNOi.
-
I-C-
-
-
I
-
=
----
-
@G
v90s.
Es= - 12 200.ca.
---
---~-
·
-
-
--- _--^
~-~---Y·-----·~---·-·-
An Equihibrium of Siver Nitf·te- and Some Fre EnergxyYates.
1Lch,
.RAbegg_ _nd Has
Lint er stch
Das Nitrition und
Etektroafinitat deY Anione-n, 7I,
sein
Q\eiChIgewicht
ngen [Lber die
mit Nitryat and WJO.
Ztschr. anorg. Chem.
,51,
-28. 190 .G(1-20, 27-28).
JCefnrn o4 AlmentoVs&4/ aoi/*John
rvon aszAkt-sAwi, Uber
dlie Diazotieruvrg des Anilins.
Ztschr. phys. Chem.
44./
Parac&ZI
n
bec~:infj~issiL~c~
Ser. 38,
(7:
A
anct'
22, 145- i9. 1897.
Ado/i,Rj;cker-, Uber
des Sillbenitrifts d~lroh
S9
-Z2. 9%5
/ Pic ,
un&c
dy
0
(14G- 148)
LOsichkeit-
Pber nitrat
19o5.
L~s;&jYAi~ck
bZn~+$~lSSLrn
i3~.92
bey nnitr-ts
e.
38 "- 7\-257I
11111111~-----_______
-·
.
___
~---·
--
--
--
I-·I--- 1~-
31.
An Equilibrium of Silver Nitrite and Some Free Energy Val es.
Bibiography (continu ed): /ilbertYerto'on
LIewIs, The Potential o- the
Oxygen E lectrode.
J. Am. Chem. Soc.
28,
158 -171.
1906. (1GB- 19g).
4.3.Ssaposhni/row, The Equilibrium of Nitrous
AcidL with Nitric Acict, Niti c, Oxice and. W&ter.
J. Ru.ss. phys.chem. Qes. 33, 50S-51G. 190L..(50G).