The d-Block Elements.
I-III B groups
PhD. Halina Falfushynska
Group 1B: Cu, Ag, and Au
• The group 1B metals are called coinage
metals because of their use in money.
• Group 1B is often found as the free metals, and are
difficult to oxidize.
• Residential electrical wiring is almost always
made of copper.
• Silver and gold are used in electronic
components, but the primary
use of gold is as a monetary
reserve for individuals and nations.
Azurite (Cu3(CO3)2(OH)2)
Cu extraction
• Chalcopyrite (CuFeS2) and chalcocite (Cu2S) minerals
are concentrated from crushed ores to the level of 10–
15% copper by froth flotation or bioleaching.
• 2СuFeS2 + O2  Cu2S + FeS + SO2
• Heating this material with silica in flash smelting
removes much of the iron as slag. FeO + SiO2  FeSiO3
• The copper matte consisting of Cu2S is convert into
oxides: 2 Cu2S + 3 O2 → 2 Cu2O + 2 SO2
• The cuprous oxide is converted
to blister copper upon heating:
2 Cu2O → 4 Cu + O2
Gold extraction
• 4Au + 8NaCN + 2H2O + O2  4Na[Au(CN)2]+
4NaOH
• 2Na[Au(CN)2] + Zn  Na2[Zn(CN)4] + 2Au
GOLD NUGGET FROM JAPAN
Group 1B: Cu, Ag, and Au
• None of these metals dissolves in HCl. Cu
and Ag dissolve in HNO3 and H2SO4
Cu + 2H2SO4CuSO4 + SO2 + 2H2O
Ag + 2HNO3 AgNO3 + NO2 + H2O
2Ag + 2H2SO4Ag2SO4 + SO2 +2H2O
• Gold requires aqua regia—a mixture of HCl
and HNO3—to dissolve.
Au + HNO3 + 4HCl  H[AuCl4] + NO + 2H2O
Properties of Group 1B
• Gold resists air oxidation. Silver forms Ag2S
(black) and copper forms Cu(OH)2·CuCO3
(green) in moist air. 2Ag + H2S  Ag2S + H2
---Gold interacts with iodine
2Au + I2  2AuI
2AuI + NaHSO3 + H2O  2Au + NaHSO4 + 2HI
---AgNO3 + Cu 
Cu(NO3)2 + Ag
Test reaction for copper
Сu2+ + S2–  CuS – black ppt;
Cu2+ + 2OH–  Cu(OH)2 – blue ppt
Сu(OH)2  CuO + H2O – black ppt;
2Cu2+ + 2SO42– + 2NH4OH  Cu2(OH)2SO4 +
2NH4+ + SO42– – green ppt
• Cu2(OH)2SO4 + 2NH4+ + 6NH3  2[Cu(NH3)4]2+ +
SO42– + 2H2O – deep blue ppt;
• Carbonates of alkali metals with Cu2+ form
greenish ppt Cu2(OH)2CO3
•
•
•
•
Biological role of copper
• Copper proteins have diverse roles in biological
electron transport and oxygen transportation,
processes that exploit the easy interconversion of
Cu(I) and Cu(II).
• Copper is also a component of other proteins
associated with the processing of oxygen
(cytochrome c oxidase, superoxide dismutases)
• Copper is an essential trace element in plants and
animals, but not some microorganisms
Biological role of copper
• Because of its role in facilitating iron uptake, copper
deficiency can produce anemia-like symptoms,
neutropenia, bone abnormalities, hypopigmentation,
impaired growth, increased incidence of infections,
osteoporosis, and abnormalities in glucose and
cholesterol metabolism. Conversely, an accumulation
of copper in body tissues causes Wilson's disease.
• Copper doorknobs are used by hospitals to reduce
the transfer of disease, and Legionnaires' disease is
suppressed by copper tubing in plumbing systems
Application of Group 1B
• CuSO4·5 H2O is used in electroplating and
batteries. Copper(II) is an essential element at
low concentrations but is toxic at higher
concentrations and is used as a pesticide.
• AgNO3 is used in photography, silver plating,
and in silvering mirrors.
• Gold compounds are used in
electroplating, photography, medicinal
chemistry, and in ruby glass and ceramics.
Group 12 element
Mercury
Copernic
ium
Name
Zinc
Cadmium
Melting
point
693 K (420
°C)
594 K (321 °C) 234 K (−39 °C)
?
Boiling point
1180 K (907
°C)
1040 K (767
°C)
630 K (357 °C)
?
Density
7.14 g·cm−3
8.65 g·cm−3
13.534 g·cm−3
?
Appearance silver-gray
silvery bluishsilvery
gray metallic
?
Atomic
radius
155 pm
?
135 pm
150 pm
Zinc production
• Roasting converts the zinc sulfide concentrate
produced during processing to zinc oxide:
2 ZnS + 3 O2 → 2 ZnO + 2 SO2
• For further processing two basic methods are
used: pyrometallurgy or electrowinning.
2 ZnO + C → 2 Zn + CO2
2 ZnO + 2 CO → 2 Zn + 2 CO2
Electrowinning processing
• Electrowinning processing leaches zinc from
the ore concentrate by sulfuric acid:
• ZnO + H2SO4 → ZnSO4 + H2O
• After this step electrolysis is used to produce
zinc metal.
• 2 ZnSO4 + 2 H2O → 2 Zn + 2 H2SO4 + O2
Typical reaction for zinc
• Reaction of zinc with air: 2Zn(s) + O2(g) → 2ZnO(s)
• Reaction of zinc with water – no reaction!
• Reaction of zinc with the halogens
Zn(s) + Br2(g) → ZnBr2(s); Zn(s) + I2(g) → ZnI2(s)
• Reaction of zinc with acids
Zn(s) + H2SO4(aq) → Zn2+(aq) + SO42-(aq) + H2(g)
• Reaction of zinc with bases
[Zn(OH)4]2-
Biological role of zinc
• In humans, zinc plays "ubiquitous biological roles". It interacts
with "a wide range of organic ligands", and has roles in the
metabolism of RNA and DNA, signal transduction, and gene
expression. It also regulates apoptosis. A 2006 study estimated
that about 10% of human proteins (2800) potentially bind zinc,
in addition to hundreds which transport and traffic zinc; a
similar in silico study in the plant Arabidopsis thaliana found
2367 zinc-related proteins.
• There are 2–4 grams of zinc distributed throughout the human
body. Most zinc is in the brain, muscle, bones, kidney, and liver,
with the highest concentrations in the prostate and parts of
the eye. Semen is particularly rich in zinc, which is a key factor
in prostate gland function and reproductive organ growth.
Dietary intake of zinc
• In the U.S., the Recommended
Dietary Allowance (RDA) is
8 mg/day for women and
11 mg/day for men. Median
intake in the U.S. around 2000
was 9 mg/day for women and
14 mg/day in men. Oysters,
lobster and red meats, especially
beef, lamb and liver have some of
the highest concentrations of zinc
in food.
zinc gluconate
Zinc supplement
• Zinc is included in most single tablet over-thecounter daily vitamin and mineral
supplements. Preparations include zinc oxide,
zinc acetate, and zinc gluconate.
• It is believed to possess antioxidant
properties, which may protect against
accelerated aging of the skin and muscles of
the body; studies differ as to its effectiveness.
• Zinc also helps speed up the healing process
after an injury.
zinc glycinate
Zinc supplement
• A 1998 review concluded that zinc oxide, one of the
most common supplements in the United States, and
zinc carbonate are nearly insoluble and poorly
absorbed in the body. For fortification, however, a
2003 review recommended zinc oxide in cereals as
cheap, stable, and as easily absorbed as more
expensive forms.
• A 1987 study found that zinc picolinate was better
absorbed than zinc gluconate or zinc citrate. However,
a study published in 2008 determined that zinc
glycinate is the best absorbed of the four dietary
supplement types available.
Zinc deficiency
• Nearly two billion people in the developing
world are deficient in zinc. In children it causes
an increase in infection and diarrhea,
contributing to the death of about 800,000
children worldwide per year. The World Health
Organization advocates zinc supplementation for
severe malnutrition and diarrhea.
• Zinc supplements help prevent disease and
reduce mortality, especially among children with
low birth weight or stunted growth