Chemistry of Chromium

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Nov 28, 2015
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Chromium is the 24th element in the periodic table and it is found in about 0.0122% of the
Earth's crust. It is named after the Greek word "chroma," meaning color. This element produces
many beautifully colored compounds, as well as a wide array of colored solutions. Chromium is
also a very useful industrial metal.

Introduction
Discovered in 1797 by Louis-Nicholas Vauquelin and isolated a year later, chromium is a very
hard steel-gray metal which takes its name from the Greek word chroma, for "color", suggesting
the wide variety of colors which characterize its compounds, many of which are used as oil paint
pigments. the pure metal is also a valuable alloying agent for spring steels and along with nickel,
in stainless steels. Chromium(III) oxide (a popular green pigment) is the ninth most abundant
chemical in the earth's crust.

 3rdC BC - According to archaeologists, Qin Dynasty and the Terracotta Army weapons
were coated with Chromium.
 1761 - Johann Gottlob Lehmann found an orange-red metal in the Ural Mountains which
was later found to be Lead chromate.
 1770 - Peter Simon Pallas came to the site where Lehmann found the metal and Pallas
found the metal to be useful in paint.
 1797 - Louis Nicolas Vauquelin discovered that he could isolate metallic chromium by
heating the oxide in a charcoal oven. This lead to the discovery of chromium metal.
 1800s - Chromium was commonly used in paints and tanning salts.
 Today - Chromium is now commonly used as metal alloys and in industrial factories.

Properties of Chromium
General Properties

Name Chromium (Cr)

 Element Group Group 6 of the
Transition Metals

Atomic Number 24

Molecular Weight 51.9961 g mol-1

Electron [Ar] 3d5 4s1

Configuration

Common Oxidation +2, +3, +6

States

Other Oxidation +1, +4, +5

States

Physical Properties

Natural State Solid

Density 7.19 g cm-3

Melting Point 2180 K

Boiling Point 2944 K

Specific Heat Capacity 23.35 J mol-1 K-1

Atomic Properties

Electronegativity 3.72 eV

Electron Affinity 64.3 kJ mol-1

 Radius 124.9 pm

Ionization Energy 652.7 kJ mol-1

Common Ions Cr2+, Cr3+, Cr6+

Metallic Properties
Chromium is a blue- gray metal that can be polished to achieve a high shine. It is extremely
lustrous and while it is relatively hard, it is also very brittle. Chromium is a fairly active metal.
While it does not react with water, it does react with most acids. It reacts with oxygen at room
temperature to form chromium (III) oxide. One of chromium's most important properties is its
self passivation. While it is stable in air, chromium will oxidize to form a thin layer that acts as a
protective coating to prevent further corrosion.

Magnetic Properties
Chromium is in elemental form, it displays paramagnetic properties. Recently, it has been
discovered that chromium can display different magnetic properties depending on its heating and
cooling, which affects the electrons' spinning alignments. Compounds of chromium, such as
chromium dioxide, are considered to be ferromagnetic. The ferromagnetic properties of these
compounds allow them to be used in data tape, a way to store information. Chromium can be
added to other compounds while maintaining its magnetic properties, and this depends on the
quantity of other elements in the compound. For example, some stainless steel compounds are
magnetic depending on the amount of chromium they contain.

Isotopes of Chromium
Chromium forms over 20 different isotopes. Three of them are considered stable while nineteen
are considered to be radioactive, and many have half lives shorter than 24 hours. The ones listed
below are the most stable and the most commonly found.

Isotopes Half-life

48
Cr 21.56 hours

49
Cr 42.3 mins
 50
Cr 1.8 x 1017 years

51
Cr 27.7025 days

52
Cr Stable

53
Cr Stable

54
Cr Stable

Occurrences of Chromium
Chromium is almost never found in its elemental state in nature, with the exception of a diamond
deposit in Russia. However, this diamond deposit has a reducing environment, which helps
produce small quantities of elemental chromium. Commonly it is found in numerous ores,
usually in the mineral chromite. Chromite is the complex of FeCr2O3FeCr2O3, or iron
chromium oxide. Chromium is also found in other minerals, including magnesiochromite
(MgCr2O4MgCr2O4). Chromite is found in earth's mantle and is mined most abundantly in
South Africa, India, Kazakhstan and Zimbabwe. Through the refining processes, chromite
produces both ferrochromium and metallic chromium.

Similar in characteristics and practical uses to vanadium and titanium, pure chromium has a
blue-white color. It is very brittle and corrosion resistant. It has three common oxidation states:
+2, +3, and +6. The metal ore (principally chromite, FeCr2O4FeCr2O4), is refined by heating in
the presence of Si or Al. The resulting ferrosilicon or ferroaluminum compound is separated from
the chromium by electrolysis.

Table 1: Chromium is found in many different

compounds, all with different uses and properties.

Oxid Compounds
ation
State

-2 Na2[Cr(CO)5]Na2[Cr(CO)5]
 -1 Na2[Cr(CO)10]Na2[Cr(CO)10]

0 Cr(CO)6Cr(CO)6

+1

+2 CrOCrO, CrF2CrF2, CrCl2CrCl2, CrSCrS,

Cr2(SO4)3Cr2(SO4)3

+3 Cr2O3Cr2O3, CrF3CrF3, CrCl3CrCl3, [Cr(

H2O)6]3+[Cr(H2O)6]3+

+4 CrO2CrO2, CrF4CrF4

+5 CrF5CrF5

+6 CrO3CrO3, Na2Cr2O7Na2Cr2O7, CrO2−4

CrO42−, CrOF4CrOF4

Chromium Oxides and Hydroxides

Chromium will form many different oxides that exhibit general acid-base behavior as well as
displaying a range of different colors.

Chromium (II) oxide

Chromium (II) oxide, CrO, is basic. It is found in the form of an insoluble black powder.

Chromium (III) oxide

Chromium (III) oxide, Cr2O3 is the main oxide of chromium. It is amphoteric and while it is
insoluble in water, it will dissolve in acid. It is found in nature in the form of a rare mineral,
eskolaite. It is used as a pigment, producing a dark green color.
Chromium dioxide
Chromium dioxide or chromium (IV) oxide, CrO2, in its natural state looks like black crystals. It
exhibits ferromagnetic properties and was once widely used as a synthetic magnet in magnetic
data tape such as audio cassette tapes. It was considered to be one of the most perfect magnetic
pigments for recording tapes because of its thin, long, glass rod like crystals. This amorphous
solid can be formed through the thermal decomposition of dichromate complexes.

Chromium trioxide
Chromium trioxide or chromium (VI) oxide, CrO3 is acidic oxide, or acidic anhydride of chromic
acid. It will react with water to form chromic acid and will react with a base to form a chromium
salt. In solid form, it is a dark red-orange granular complex. It is used in chrome-plating as a
strong oxidizer, however, it is extremely toxic.

Chromate and Dichromate

Chromate, CrO42-, is a salt of chromic acid. This salt is associated with a yellow color in basic
conditions, for example potassium chromate. Dichromate, Cr 2O72-, is a salt of dichromic acid.
This salt is associated with a strong orange color in acidic conditions, for example potassium
dichromate. However, compounds of chromate or dichromate with heavy metals usually display
a red color. Dichromate is a strong oxidizing agent but it is a bad precipitating agent. Chromate
on the other hand is used as a precipitating agent but it is a poor oxidizing agent. Chemical
equilibrium is displayed when either anion is in an aqueous solution.

2CrO2−4(s)+2H+(aq)⇌H2O(l)+Cr2O2−7(aq)Kc=3.2×10142CrO4(s)2−+2H(aq)+⇌H2O(l)
+Cr2O7(aq)2−Kc=3.2×1014

In acidic solution, the forward reaction is favored. In basic solution, the reverse reaction is
favored.
Passivation of Chromium
Chromium is one of the few metals that has the property of passivation. Chromium will
spontaneously react to form a thin layer of oxide that protects the metal against further corrosion.
This surface is hard and nonreactive. This makes chromium ideal for electroplating other metals
to protect them from oxidizing, and because of it's hardness, it is used to harden the surface of
many objects, such as metal tools.

Quintuple Bond
First discovered in 2005, Chromium, Molybdenum, Tungsten, and Rhenium, all have a special
ability to form a quintuple bond; also known as a five fold bond. In Chromium cases, di-
chromium was discovered to have a quintuple bond, which means that 10 electrons are
participating in the bond with metal - metal. Chromium uses terphenyl ligand to perform this
action, thus making it relatively weak, but stable up to 200°C. A quintuple bond is only possible
if chromium atom has only one other ligand in order to keep the bond stable. Although the
discovery is fairly recent, it has already provided great insight as to how transition metals are
able to bond with each other.

Production of Chromium
Chromium is produced from mined minerals such as chromite. The processes used to extract
chromium are similar to those of other metals. Chromium oxides can be heated with other
substances such as charcoal or aluminum. Through the process of heating, the carbon or
aluminum form oxides, leaving chromium in pure metal form. Pure chromium can also be
produced by running an electric current through some of its compounds. These are just two ways
of extracting chromium from its compounds. There are other processes to extract chromium such
the Thermite Process:

Fe2O3+2Al→2Fe+Al2O3Fe2O3+2Al→2Fe+Al2O3

Chromite and Ferrochromium can also be used directly to add chromium to other substances
such as steel.

Applications of Chromium
Chromium has many applications. It has been used in dyes to act as a mordant, which will
permanently fix dyes to different fabrics. Chromium has also been used in paints as pigments.
This is because chromium exhibits many different colors including; black, gray, green, blue,
violet, orange, yellow and red, depending on the compound. Chromium is used as an additive to
stainless steel, giving the steel its "stainless" property. Because chromium is self-passivating, it
will add a protective layer to the steel. It also acts to harden the steel. Stainless steel containing
chromium is a very useful alloy and is used in safes, ball bearings, and surgical tools.

Chrome plating is another application of chromium's self passivation. Metals and other
substances are chrome plated to add a protective and attractive outer coat. Chromium metal can
be polished to a high shine which will make the metal more attractive. The magnetic properties
of chromium make it perfect for magnetic tapes. Chromium dioxide is used in recording tapes.
Potassium dichromate has been used in the tanning of leather. Small trace quantities of
chromium have been found in semiprecious stones including: rubies, sapphires, emeralds,
serpentine and jade. Chromium is also used to line ovens and molds because of its high melting
point. This element is even found in the human body. Chromium is common in small quantities
in the body and has been connected to the body's use of sugar. It is commonly found in foods
such as romaine lettuce, onions and tomatoes. A deficiency of chromium leads to symptoms that
are commonly seen in diabetics. Although chromium is good in small quantities, larger quantities
of chromium can be extremely harmful to humans.

Problems
Answer the following:

1. Write the reaction for chromium (VI) equilibrium in aqueous solutions.

2. List different oxidation states of chromium and examples of compounds they form.
3. Who first made chromium in its metallic form?
4. List different oxides of chromium.
5. What is chromium's symbol, atomic number and weight?
6. What are some common uses of chromium today?
7. What is the magnetic property of chromium?
8. Write out the electron configuration of: Cr, Cr6+, Cr2+.
9. Why is passivation an important property of chromium?
10. What are some of the uses of chromium today?

Sumber :
https://chem.libretexts.org/Core/Inorganic_Chemistry/Descriptive_Chemistry/Elements_Organized_by_
Block/3_d-Block_Elements/Group_06%3A_Transition_Metals/Chemistry_of_Chromium
Chromium

Chromium is thought to influence how the hormone insulin behaves in the body. This means

chromium may affect the amount of energy we get from food.

Good sources of chromium

Good sources of chromium include:

 meat

 wholegrains – such as wholemeal bread and whole oats

 lentils

 broccoli

 potatoes

 spices

How much chromium do I need?

Around 25mcg of chromium a day should be enough for adults.

You should be able to get all the chromium you need by eating a varied and balanced diet.

What happens if I take too much chromium?

There's not enough evidence to know what the effects might be of taking high doses of

chromium each day.

What does the Department of Health advise?

You should be able to get all the chromium you need by eating a varied and balanced diet.
If you take chromium supplements, don't take too much as this might be harmful.

Having 10mg or less a day of chromium from food and supplements is unlikely to cause any

harm.

Sumber : https://www.nhs.uk/conditions/vitamins-and-minerals/others/#chromium

6. ESSENTIAL NUTRIENTS - MINERALS

6.1 Introduction and classification

With the exception of the organically bound elements hydrogen, carbon, nitrogen and oxygen, there are
about 20 or so inorganic mineral elements which are considered to be essential to animal life, including
fish and shrimp. The essential mineral elements are usually classified into two main groups according to
their concentration in the animal body; the macroelements and the microelements (Table 11)

Table 11. The essential mineral elements 1

Macroelements
Trace or microelements
Principal cations Principal anions

Calcium (Ca) Phosphorus (P) Iron (Fe) Fluorine (F)

Magnesium (Mg) Chlorine (Cl) Zinc (Zn) Vanadium (V)

Sodium (Na) Sulphur (S) Manganese (Mn) Chromium (Cr)

Potassium (K) Copper (Cu) Molybdenum (Mo)

Iodine (I) Selenium (Se)

Cobalt (Co) Tin (Sn)

Nickel (Ni) Silicon (Si)

1
Underwood (1971); Reinhold (1975)

6.2 General function

The general function of minerals and trace elements can be summarised as follows:
  Minerals are essential constitutents of skeletal structures such as bones and teeth.

 Minerals play a key role in the maintenance of osmotic pressure, and thus regulate the exchange
of water and solutes within the animal body.

 Minerals serve as structural constituents of soft tissues.

 Minerals are essential for the transmission of nerve impulses and muscle contraction.

 Minerals play a vital role in the acid-base equilibrium of the body, and thus regulate the pH of the
blood and other body fluids.

 Minerals serve as essential components of many enzymes, vitamins, hormones, and respiratory
pigments, or as cofactors in metabolism, catalysts and enzyme activators.

6.3 Macroelements

6.3.1 Calcium

Biological function: The principal biological functions of calcium may be summarised as follows;

 Calcium is an essential component of bone, cartilage and the crustacean exoskeleton.

 Calcium is essential for the normal clotting of blood, by stimulating the release of thromboplastin
from the blood platelets.

 Calcium is an activator for several key enzymes, including pancreatic lipase, acid phosphatase,
cholinesterase, ATPases, and succinic dehydrogenase.

 Through its role in enzyme activation, calcium stimulates muscle contraction (ie. promotes
muscle tone and normal heart beat) and regulates the transmission of nerve impulses from one
cell to another through its control over acetylcholine production.

 Calcium, in conjunction with phospholipids, plays a key role in the regulation of the permeability
of cell membranes and consequently over the uptake of nutrients by the cell.

 Calcium is believed to be essential for the absorption of vitamin B12 from the gastro-intestinal
tract.

Dietary sources and absorption: Rich dietary sources of calcium include limestone, oystershell grit, bone
meal, rock phosphate (40–30%); crab meal, shrimp meal, meat and bone meal (20–10%); white fish meal,
poultry manure, meat meal (10–5%); and brown fish meal, delactose whey powder, dried skim milk,
poultry by-product meal, kelp meal, alfalfa meal (5–1%).

Calcium is readily absorbed through the gastro-intestinal tract (through vitamin D 3 action), gills, skin and
fins of fish and crustacea. In general, dietary calcium absorption is facilitated by dietary lactose (by
forming a soluble sugar-calcium complex) and by high gastric acidities (by aiding solubilization of the
calcium salt).
6.3.2 Phosphorus

Biological function: The principal biological functions of phosphorus may be summarized as follows;

 Phosphorus is an essential component of bone, cartilage and the crustacean exoskeleton.

 Phosphorus is an essential component of phospholipids, nucleic acids, phosphoproteins (casein),

high energy phosphate esters (ATP), hexose phosphates, creatine phosphate, and several key
enzymes.

 As a component of these important biological substances, phosphorus plays a central role in

energy and cell metabolism.

 Inorganic phosphates serve as important buffers to regulate the normal acidbase balance (ie. pH)
of animal body fluids.

Dietary sources and absorption: Rich dietary sources of phosphorus include rock phosphate, dicalcium
phosphate, bone meal (20–10% P); meat and bone meal, meat meal, white fish meal, shrimp meal, poultry
by-product meal, dried poultry manure (5–2%); and rice bran, rice polishings, wheat bran, wheat mill run,
dried brewers yeast, sunflower seed meal, cottonseed meal, rapeseed meal, sesame seed meal, dried
delactose whey (2–1%).

Although soluble phosphorus salts can be absorbed through the skin, fins and gills of fish and shrimp, the
concentration of phosphorus in fresh and sea water is low, and consequently body phosphorus
requirements are usually met from dietary sources. Within plant foods, including cereals and oilseeds, 50–
80% of the phosphorus occurs in the form of the calcium or magnesium salt of phytic acid; phytic acid
being the hexaphosphate ester of inositol. This organic form of phosphorus must first be hydrolyzed
within the gastro-intestinal tract by the enzyme phytase to inositol and phosphoric acid before it can be
utilized and absorbed by the animal. As with calcium, the absorption of inorganic phosphorus salts is
facilitated by high gastric acidity; the more soluble the salt the higher the availability and absorption of
phosphorus.

6.3.3 Magnesium

Biological function: The principal biological functions of magnesium may be summarised as follows;

 Magnesium is an essential component of bone, cartilage and the crustacean exoskeleton.

 Magnesium is an activator of several key enzyme systems, including kinases, (ie. enzymes that
catalyse the transfer of the terminal phosphate of ATP to sugar or other acceptors), mutases
(transphosphorylation reactions), muscle ATPases, and the enzymes cholinesterase, alkaline
phosphatase, enolase, isocitric dehydrogenase, arginase (magnesium is a component of the
arginase molecule), deoxyribonuclease, and glutaminase.

 Through its role in enzyme activation, magnesium (like calcium) stimulates muscle and nerve
irritability (contraction), is involved in the regulation of intracellular acid-base balance, and plays
an important role in carbohydrate, protein and lipid metabolism.
Dietary sources and absorption: Rich dietary sources of magnesium include; meat and bone meal, rice
bran, kelp meal, sunflower seed meal (1.0–0.75% Mg); and wheat bran, wheat mill run, rice polishings,
rapeseed meal, shrimp meal, cottonseed meal, linseed meal, poultry manure and crab meal (0.75–0.5%).

Magnesium is readily absorbed through the gastro-intestinal tract, gills, skin and fins of fish and
crustacea. As with calcium and phosphorus, a proportion of the magnesium contained in plant foodstuffs
may be present in the form of phytin (Ca or Mg salt of phytic acid).

6.3.4 Sodium, Potassium and Chlorine

Biological function: Sodium, potassium, and chlorine occur almost entirely in the fluids and soft tissues
of the body, sodium and chlorine being found mainly in the body fluids, and potassium occuring mainly
in the cells. They serve a vital function in controlling osmotic pressures and acid-base equilibrium. They
also play important roles in water metabolism.

Sodium is the main monovalent ion of extracellular fluids; sodium ions constituting 93% of the ions
(bases) found in the blood stream. Although the principal role of sodium in the animal is connected with
the regulation of osmotic pressure and the maintenance of acid-base balance, sodium also has an effect on
muscle irritability, and plays a specific role in the absorption of carbohydrate.

Potassium is the major cation of intracellular fluid, and regulates intracellular osmotic pressue and acid-
base balance. Like sodium, potassium has a stimulating effect on muscle irritability. Potassium is also
required for glycogen and protein sysnthesis, and the metabolic breakdown of glucose.

Chlorine is the main monovalent anion of extracellular fluids; chlorine ions constituting about 65% of the
total anions of blood plasma and other extracellular fluids within the body (ie. gastric juice). Chlorine is
therefore essential for the regulation of osmotic pressue and acid-base balance. Chlorine also plays a
specific role in the transport of oxygen and carbon dioxide in the blood, and the maintenance of digestive
juice pH.

Dietary sources and absorption: Rich dietary sources of sodium, potassium and chlorine include: kelp
meal, condensed fish solubles, dried delactose whey, shrimp meal, white fish meal, meat meal, meat and
bone meal (4–1% Na in decreasing order); dehydrated cane molasses, condensed fish solubles, delactose
whey powder, alfalfa meal, dried torula yeast, soybean meal, rice bran (4-2% K in decreasing order);
dried brewers yeast, dried distillers solubles, wheat bran, cottonseed meal, meat and bone meal, wheat
mill run, copra meal, rapeseed meal, peanut meal, and sunflower seed meal (2–1% K in decreasing order);
salt (sodium chloride, 60% Cl) and potassium chloride (48% Cl).

Potassium, sodium and chloride are readily absorbed from the gastrointestinal tract, skin, fins and gills of
fish and crustacea.

6.3.5 Sulphur

Biological function: The principal biological functions of sulphur may be summarised as follows;

 Sulphur is an essential component of several key amino acids (methionine and cystine), vitamins
(thiamine and biotin), the hormone insulin, and the crustacean exoskeleton.

 As the sulphate, sulphur is an essential component of heparin, chondroitin, fibrinogen and taurine.
  Several key enzyme systems such as coenzyme A and glutathione depend for their activity on free
sulphydryl (SH) groups.

 Sulphur is believed to be involved in the detoxification of aromatic compounds within the animal
body.

Dietary sources and absorption: Rich dietary sources of the sulphur containing amino acids include fish
meal, chicken eggs, and hydrolysed feather meal (the latter containing primarily cystine, Table 5).
Sulphur containing amino acids and to a lesser extent inorganic sulphates are readily absorbed from the
gastrointestinal tract of fish and shrimp.

6.4 Microelements

6.4.1 Iron

Biological function: The principal biological functions of iron may be summarised as follows;

 Iron is an essential component of the respiratory pigments haemoglobin and myoglobin.

 Iron is an essential component of various enzyme systems including the cytochromes, catalases,
peroxidases, and the enzymes xanthine and aldehyde oxidase, and succinic dehydrogenase.

 As a component of the respiratory pigments and enzymes concerned in tissue oxidation, iron is
essential for oxygen and electron transport within the body.

Dietary sources and absorption: Rich dietary sources of iron include; blood meal (0.3–0.2% Fe); kelp
meal, coconut meal, meat and bone meal, sunflower seed meal, dried distillers solubles (1000–500
mg/kg); alfalfa meal, crab meal, condensed fish solubles, fish meal, meat meal, poultry by-product meal,
linseed meal, dried brewers yeast, dehydrated cane molasses, rice bran, delactose whey powder, and dried
poultry manure (500–200 mg/kg).

Iron is readily absorbed through the gastro-intestinal tract, gills, fins and skin of fish and crustacea.
Dietary iron availability and absorption is usually depressed by high dietary intakes of phosphate,
calcium, phytates, copper and zinc. In general, inorganic sources of iron are more readily absorbed than
organic sources; the ferrous iron (Fe++) being more available for absorption than ferric iron (Fe+++).
Reducing substances such as vitamin C enhance the absorption of non-haem iron.

6.4.2 Zinc

Biological function: The principal biological functions of zinc may be summarised as follows;

 Zinc is an essential component of more than 80 metalloenzymes, including carbonic anhydrase

(required for the transport of carbon dioxide by the blood and for the secretion of HCI in the
stomach), glutamic dehydrogenase, alkaline phosphatase, pyridine nucleotide dehydrogenase,
alcohol dehydrogenase, superoxide dismutase, pancreatic carboxypeptidase, and tryptophan
desmolase.
  Zinc serves as a cofactor in many enzyme systems, including arginase, enolase, several
peptidases, and oxalacetic decarboxylase.

 As an active component or cofactor for many important enzyme systems zinc plays a vital role in
lipid, protein, and carbohydrate metabolism; being particularly active in the synthesis and
metabolism of nucleic acids (RNA) and proteins.

 Although not proven, it has been suggested that zinc plays a role in the action of hormones such
as insulin, glucagon, corticotrophin, FSH and LH.

 Zinc is believed to play a positive role in wound healing.

Dietary sources and absorption: Rich dietary sources of zinc include chick hatchery meal (0.15% Zn),
dried Candida yeast, dehydrated fish solubles, dried distillers grains with solubles, dried poultry manure
(500–200 mg/kg); fish meal, corn gluten meal, poultry by-product meal, wheat bran, rice mill run,
dehydrated cattle manure, wheat middlings, crab meal, sunflower seed meal, dried torula yeast (200–100
mg/kg Zn).

Zinc is readily absorbed from the gastro-intestinal tract, gills, fins and skin of fish and crustacea. Dietary
zinc availability and absorption is reduced in the presence of phytates, and high dietary intakes of
calcium, phopshorus and copper.

6.4.3 Manganese

Biological function: The principal biological functions of managanese may be summarised as follows,

 Manganese functions in the body as an enzyme activator for those enzymes that mediate
phosphate group transfer (ie. phosphate transferases and phosphate dehydrogenases), particularly
those concerned with the citric acid cycle including arginase, alkaline phosphatase and
hexokinase.

 Manganese is an essential component of the enzyme pyruvate carboxylase

 As a cofactor or component of several key enzyme systems, manganese is essential for bone
formation (re. mucopolysaccharide synthesis), the regeneration of red blood cells, carbohydrate
metabolism, and the reproductive cycle.

Dietary sources and absorption: Rich dietary sources of manganese include kelp meal (0.10% Mn), rice
bran, dehydrated poultry manure, palm kernel meal, crab meal, wheat bran, wheat germ meal, wheat mill
run, wheat middlings (300–100 mg/kg); dehydrated cattle manure, corn distillers dried solubles, rye grain,
dehydrated cane molasses, dehydrated fish solubles, copra meal (100–50 mg/kg); wheat, rapeseed meal,
sesame seed meal, linseed meal, brewers dried grains, safflower seed meal, shrimp meal and oats (50–30
mg/kg).

Manganese is readily absorbed from the gastro-intestinal tract, gills, fins and skin of fish and crustacea.
Dietary manganese availability and absorption is reduced in the presence of phytates, and high dietary
intakes of calcium.

6.4.4 Copper
Biological function: The principal biological functions of copper may be summarised as follows;

 Copper is an essential component of numerous oxidation-reduction enzyme systems. For

example, copper is a component of the enzymes cytochrome oxidase, uricase, tyrosinase,
superoxide dismutase, amine oxidase, lysyl oxidase, and caeruloplasmin.

 As a component of the enzyme caeruloplasmin (ferroxidase), copper is intimately involved with

iron metabolism, and therefore haemoglobin synthesis and red blood cell production and
maintenance.

 Copper is also believed to be necessary for the formation of the pigment melanin and
consequently skin pigmentation, for the formation of bone and connective tissue, and for
maintaining the integrity of the myelin sheath of nerve fibres.

Dietary sources and absorption: Rich dietary sources of copper include condensed fish solubles, corn
distillers dried solubles, dehydrated sugar cane molasses (100-75 mg/kg Cu); corn distillers grains with
solubles, dehydrated poultry manure (75–50 mg/kg); dried brewers yeast, crab meal, corn gluten meal,
linseed meal, soybean meal, dried brewers grains, wheat mill run, millet, cottonseed meal, wheat
middlings, and copra meal (50–20 mg/kg).

Copper is readily absorbed from the gastro-intestinal tract, gills, fins and skin of fish and crustacea.
Dietary copper availability and absorption is reduced in the presence of phytates, and high dietary intakes
of zinc, iron, molybdenum, cadmium, inorganic sulphates and calcium carbonate.

6.4.5 Cobalt

Biological function: The principal biological functions of cobalt may be summarised as follows;

 Cobalt is an integral component of cyanocobalamin (vitamin B12), and as such is essential for red
blood cell formation and the maintenance of nerve tissue.

 Although not confirmed, cobalt may also function as an activating agent for various enzyme
systems.

Dietary sources and absorption: Rich dietary sources of cobalt include copra meal (2 mg/kg Co), linseed
meal, dried brewers yeast, fish meal, meat meal, cottonseed meal, and soybean meal (0.5–0.1 mg/kg).

Cobalt is readily absorbed from the gastro-intestinal tract and the surrounding water by fish and crustacea.
Dietary cobalt availability and absorption is reduced in the presence of high dietary intakes of iodine.

6.4.6 Iodine

Biological function: Iodine is an integral component of the thyroid hormones, thyroxine and tri-iodo-
thyronine, and as such is essential for regulating the metabolic rate of all body processes.

Dietary sources and absorption: Rich dietary sources of iodine include all food stuffs of marine origin,
and in particular seaweed meals (which may contain up to 0.6% I) and marine fish and crustacean meals.
Iodine is readily absorbed from the gastro-intestinal tract and the surrounding water by fish and crustacea.
Dietary availability and absorption is reduced in the presence of high dietary intakes of cobalt.
6.4.7 Selenium

Biological function: Selenium is an essential component of the enzyme glutathione peroxidase, and as
such (together with the tocopherols - vitamin E) serves to protect cellular tissues and membranes against
oxidative damage. It has also been suggested that selenium participates in the biosynthesis of ubiquinone
(coenzyme Q; involved in cellular electron transport) and influences the absorption and retention of
vitamin E.

Dietary sources and absorption: Rich dietary sources of selenium include dehydrated fish solubles, fish
meal (5–2 mg/kg Se); dried brewers yeast, corn gluten meal, dried torula yeast, rapeseed meal, cottonseed
meal (2–1 mg/kg); and dried brewers grains, wheat bran, wheat middlings, linseed meal, hydrolyzed
feather meal, poultry by-product meal, meat meal and alfalfa (1–0.5 mg/kg). Selenium is readily absorbed
from the gastro-intestinal tract and the surrounding water by fish and crustacea.

6.4.8 Chromium

Biological function: Trivalent chromium is an integral component of the glucose tolerance factor (GTF; a
low molecular weight compound with trivalent chromium coordinated to two nicotinic acid molecules
with the remaining coordinates protected by amino acids) and acts as a cofactor for the hormone insulin.
Apart from its vital role in carbohydrate metabolism (ie. glucose tolerance and glycogen synthesis),
trivalent chromium is also believed to play an important role in cholesterol and amino acid metabolism.

Dietary sources and absorption: Rich dietary sources of trivalent chromium include chick shell meal (15
mg/kg), shrimp tail meat, Artemia salina, dried brewers yeast, shellfish, liver, poultry by-product meal
and fish meal (5–1 mg/kg dry weight). Trivalent chromium is readily absorbed from the gastrointestinal
tract and the surrounding water by fish and crustacea.

6.5 Dietary mineral requirements

There is scant information on the dietary mineral requirements of fish and shrimp. This is mainly due to
complexities which arise because of the ability of aquatic animals to absorb minerals from the
surrounding water in addition to the food ingested, and because of their variation in response to salt
regulation or osmotic pressure. For example, because marine fish and shrimp live in a hypertonic
environment (ie. in a medium containing an excess of salt) they tend to suffer from dessication through
water loss across the gills. To compensate for this loss marine fish therefore have to continually drink
small amounts of water; the excess salt contained within the intestinal seawater being pumped out of the
gill to the exterior (Cowey and Sargent, 1979). Consequently, since marine fish are reported to drink up to
50 percent of their total body weight per day, drinking may satisfy a substantial part of their mineral
requirements (NRC, 1983). Coupled with the direct absorption of minerals through the gills, fins and skin,
it is perhaps not surprising that marine fish such as the red sea bream (C. major) have only been found to
have a positive dietary requirement for phosphorus, potassium and iron when fed a purified diet; the
nutritional requirement for the remaining physiologically essential minerals being apparently satisfied
through direct absorption and/or drinking (Yone and Toshima, 1979). The situation in freshwater fish and
prawns is the reverse; here the animals suffer from hydration across the gills due to the steady loss of salt
to the hypotonic environment. These animals therefore drink little or no water, and have to compensate
for their urinary salt losses by actively pumping salt from the external medium across the gills into the
plasma. Freshwater fish and prawns are therefore more demanding on an adequate dietary mineral supply
than marine fish and shrimp (Cowey and Sargent, 1979).
From the above it follows therefore that the dietary requirement of a fish or shrimp species for a particular
element will depend to a large extent upon the concentration of that element in the water body. At present
there is little information concerning the contribution of waterborne elements to the total mineral balance
of fish or shrimp (Tacon, Knox and Cowey, 1984).

Dietary mineral requirements are usually determined by feeding graded levels of each element within a
purified or semi-purified test diet; dietary requirement being taken at ‘break-point’ on the basis of the
observed growth response, feed efficiency, or tissue enzyme indicator level (for review see Cowey and
Sargent, 1972; Cho, Cowey and Watanabe, 1985; Kanazawa, 1983; Lall, 1979; Nose and Arai, 1979;
NRC, 1983; and Robinson and Wilson, 1985). As with the vitamins, the majority of studies have been
conducted under controlled laboratory conditions and so little information exists on the dietary mineral
requirements of fish or shrimp under practical semi-intensive or intensive farming conditions using
practical diets.

Despite these limitations, the known dietary mineral requirements of the major aquaculture species are
summarised in Table 12.

Table 12. Dietary mineral requirements of fish and shrimp

Species/Element Dietary requirement Reference

CALCIUM

Rainbow trout (S. gairdneri) 0.24 % Arai et al., (1975)

Eel (A. japonica) 0.27 % Arai, Nose & Hashimoto (1975)

Channel catfish (I. punctatus) ≤0.05 % Lovell & Li (1978)

Channel catfish (I. punctatus) 0.45 % 1 Robinson et al., (1985)

Channel catfish (I. punctatus) 1.50 % Andrews, Murai & Campbell (1973)

Common acrp (C. carpio) ≤0.028 % Ogino & Takeda (1976)

Red sea bream (C. major) 0.34 % Sakamoto & Yone (1973)

Red sea bream (C. major) >0.14 % Sakamoto & Yone (1976)

Penaeids (P. japonicus) 1–2 % Kanazawa, Teshima & Sasaki (1984)

Penaeids (P. japonicus) 1.24 % Kitabayashi et al., (1971)

Penaeids (P. japonicus) 1.0 % Kanazawa (1983)

Penaeids (P. japonicus) <0.5 % Deshimaru et al., (1978)

1
Dietary calcium requirement determined in calcium-free water
PHOSPHORUS

Rainbow trout (S. gairdneri) 0.70 % Ogino & Takeda (1978)

Atlantic salmon (S. salar) 1.12 % 1 Ketola (1975)

Common carp (C. carpio) 0.6–0.7 % 2 Ogino & Takeda (1976)

Tilapia (O. niloticus) ≤0.90 % 2 Watanabe et al., (1980)

Tilapia (O. aureus/niloticus) 0.45–0.6 % 2, 3 Viola, Zohar & Arieli (1986)

Eel (A. japonica) 0.29 % Arai, Nose & Kawatsu (1974)

Channel catfish (I. punctatus) 0.42 % 2 Wilson et al., (1982)

Channel catfish (I. punctatus) 0.50 % 2 NRC (1983)

Channel catfish (I. punctatus) 0.45 % 2 Lovell (1978)

Red sea bream (C. major) 0.68 % Sakamoto & Yone (1973)

Penaeids (P. japonicus) 1.04 % Kitabayashi et al., (1971)

Penaeids (P. japonicus) 2.00 % Deshimaru & Yone (1978a)

Penaeids (P. japonicus) 1.00 % Kanazawa (1983)

Penaeids (P. japonicus) 1–2 % Kanazawa, Teshima & Sasaki (1984)

1
Basal diet contained 0.62% P derived mainly from plant sources and requireda minimum of 0.6% supplemental inorganic P as dibasic calcium
phosphate formaximum growth response
2
Available phosphorus requirement (as determined with fish)
3
Experiments conducted in floating cages suspended in an earthen pond, 100 fishof average size 120g/m3, and available P requirement based on P
availabilitiesof 70% for fish meal and Dicalcium phosphate and 33% for plant phosphorus
MAGNESIUM

Rainbow trout (S. gairdneri) 0.06–0.07 % Ogino, Takashima & Chiou (1978)

Rainbow trout (S. gairdneri) 0.05 % Knox, Cowey & Adron (1981, 1983)

Common carp (C. carpio) 0.04–0.05 % Ogino & Chiou (1976)

Eel (A. japonica) 0.04 % Nose & Arai (1979)

Channel catfish (I. punctatus) 0.04 % Gatlin et al., (1982)

Red sea bream (C. major) <0.012 % Sakamoto & Yone (1979)

Penaeids (P. japonicus) 0.30 % Kanazawa (1983)

Penaeids (P. japonicus) ND 1 Deshimaru & Yone (1978a)

1
No dietary requirement demonstrated
POTASSIUM 1

Penaeids (P. japonicus) 1.0 % Deshimaru & Yone (1978a)

Penaeids (P. japonicus) 0.9 % Kanazawa (1983)

Red sea bream (C. major) 0.21 % Yone & Toshima (1979)
1
No dietary requirement or deficiency symptom demonstrated for sodium orchlorine in fish or shrimp to date
ZINC

Rainbow trout (S. gairdneri) 15–30 mg/kg Ogino & Yang (1978)

Rainbow trout (S. gairdneri) 150 mg/kg 1 Ketola (1978, 1979)

Common carp (C. carpio) 15–30 mg/kg Ogino & Yang (1979)

Channel catfish (I. punctatus) 20 mg/kg Gatlin & Wilson (1983)

Channel catfish (I. punctatus) 150 mg/kg2 Gatlin & Wilson (1984)
1
Basal practical diet containing white fish meal as the major protein sourceand 60 mg/kg Zn; diet required supplemental Zn as ZnSO 4.7H2O at
150 mg/kgdiet to prevent Zn deficiency and produce normal growth
2
Basal practical diet containing 1.1% phytic acid from soybean meal and rice,and requiring a dietary supplementation of 150 mg Zn/kg diet to
preventdeficiency symptoms
IRON

Channel catfish (I. punctatus) ≤30 mg/kg Gatlin & Wilson (1986)

Eel (A. japonica) 170 mg/kg Nose & Arai (1979)

Red sea bream (C. major) 150 mg/kg Sakamoto & Yone (1976a, 1978)

Penaeids (P. japonicus) ND1 Kanazawa, Teshima & Sasaki (1984)

1
No dietary requirement demonstrated
COPPER

Rainbow trout (S. gairdneri) 3 mg/kg Ogino & Yang (1980)

Common carp (C. carpio) 3 mg/kg Ogino & Yang (1980)

Channel catfish (I. punctatus) 5 mg/kg Gatlin & Wilson (1986a)

Penaeids (P. japonicus) 60 mg/kg Kanazawa (1983)

Penaeids (P. japonicus) ND 1 Kanazawa, Teshima & Sasaki (1984)

1
No dietary requirement demonstrated
MANGANESE

Rainbow trout (S. gairdneri) 12–13 mg/kg Ogino & Yang (1980)

Common carp (C. carpio) 12–13 mg/kg Ogino & Yang (1980)

Channel catfish (I. punctatus) ≤2.4 mg/kg 1 Robinson & Wilson (1985)

Channel catfish (I. punctatus) 25 mg/kg 2 Robinson & Wilson (1985)

1
No dietary requirement demonstrated with fish fed purified diets for 13 weeks,and containing a basal manganese content of 2.4 mg/kg (studies
in press)
2
Recommended dietary Mn level for practical catfish feeds
IODINE

Chinook salmon (O. tshawytscha) 0.6–1.1 mg/kg Woodall & LaRoche (1964)
Salmonids 1–5 mg/kg NRC (1983)

SELENIUM

Rainbow trout (S. gairdneri) 0.07–0.38 mg/kg Hilton, Hodson & Slinger (1980)

Channel catfish (I. punctatus) 0.1–0.25 mg/kg 1 Gatlin & Wilson (1984)
1
Dietary requirement of 0.25 mg/kg within purified diets, and a recommendeddietary requirement of 0.1 mg/kg Se within practical catfish feeds
CHROMIUM

Rainbow trout (S. gairdneri) ≤1.0 mg/kg Tacon & Beveridge (1982)

6.6 Mineral pathology

6.6.1 Mineral deficiency

The following gross anatomical deficiency signs have been reported in juvenile fish or shrimp fed
experimental diets lacking in one or more essential mineral elements:

Element/species Deficiency signs 1

PHOSPHORUS

Common carp (C. carpio) Reduced growth, poor feed efficiency (1,2); bone demineralization,
skeletal deformity, abnormal calcification of ribs and soft rays of
pectoral fin (1); cranial deformity (1,3); increased visceral fat (4)

Channel catfish (I. punctatus) Reduced growth, poor feed efficiency (5); bone demineralization
(5,6)

Red sea bream (C. major) Reduced growth, poor feed efficiency, bone demineralization,
increased muscle, liver and vertebrae lipid content (7); curved and
enlarged spongy vertebrae (8); decreased liver glycogen (9)

Eel (A. japonica) Anorexia, reduced growth (10)

Rainbow trout (S. gairdneri) Reduced growth, poor feed efficiency, bone demineralization (13,14)

Atlantic salmon (S. salar) Reduced growth, poor feed efficiency, bone demineralization (13,14)

Penaeids (P. japonicus) Reduced growth (41)

CALCIUM

Channel catfish (I. punctatus) Reduced growth, low carcass ash, Ca and P content (fed vitamin D
deficienct diets, 6)

Rainbow trout (S. gairdneri) Anorexia, reduced growth and feed efficiency (15)

Eel (A. japonica) Anorexia, reduced growth and feed efficiency (16)
Red sea bream (C. major)
MAGNESIUM
Common carp (C. carpio)
Channel catfish (I. punctatus)
Eel (A. japonica)
Rainbow trout (S. gairdneri)
Penaeids (P. japonicus)
IRON
ZINC
Channel catfish (I. punctatus)
Common carp (C. carpio)
Rainbow trout (S. gairdneri)
MANGANESE
Tilapia (O. mossambicus)
Common carp (C. carpio)
Rainbow trout (S. gairdneri)
COPPER
Common carp (C. carpio)
SELENIUM
Atlantic salmon (S. salar)
Common carp (C. carpio)
Anorexia, reduced growth and feed efficiency (17)
Reduced growth (11, 18); sluggishness, anorexia, convulsions, high
mortality (11); cataracts (18)
Anorexia, reduced growth, sluggishness, muscle flacidity, high
mortality (19)
Anorexia, reduced growth (20)
Reduced growth (21–24); anorexia (22,23); cataracts (25);
sluggishness, calcinosis of kidney (21,22); increased mortality,
vertebral curvature, degener- ation of muscle fibres and epithelial
cells of pyloric caecae and gill filaments (23); reduced bone ash, Mg
and elevated Ca content (24)
Reduced growth, poor survival and reduced feed efficiency (41)
Hypochromic microcytic anaemia (C. carpio - 26; C. major -
27; Salvelinus fontinalis - 28; A. japonica - 20; I. punctatus - 42;
reduced growth and feed efficiency (42)
Reduced growth, anorexia, depressed bone Ca and Zn content (29)
Reduced growth (18, 30); cataracts (18); anorexia, high mortality,
erosion of fins and skin, elevated tissue concentrations of Fe and Cu
in intestine and hepatopancreas (30)
Reduced growth (25,31,32); increased mortality (31, 32); cataracts
(25, 31); short body dwarfism (25); fin erosion (31)
Reduced growth, anorexia, loss of equilibrium, mortality (33)
Reduced growth (34, 18); short body dwarfism, cataracts (18)
Cataracts (25, 35); reduced growth, short body dwarfism (34, 35);
abnormal tail growth (34)
Reduced growth (34, 18); cataracts (18)
Increased mortality, muscular dystrophy, depressed glutathione
peroxidase activity (36)
Reduced growth (18, 37); cataracts (18); anaemia (37)
Channel catfish (I. punctatus) Reduced growth (38)

IODINE

Salmonids Thyroid hyperplasia/goitre (39, 40)

1
1-Ogino & Takeda (1976); 2-Yone & Toshima (1979); 3-Ogino et al., (1979); 4-Takeuchi & Nakazoe (1981); 5-Andrews, Murai & Campbell
(1973); 6-Lovell & Li(1978); 7-Sakamoto & Yone (1980); 8-Sakamoto & Yone (1979); 9-Sakamoto & Yone(1978); 10-Arai, Nose & Kawatsu
(1974); 11-Ogino & Chiou (1976); 12-Ogino &Takeda (1978); 13-Ketola (1975); 14-Lall & Bishop (1977); 15-Arai et al. (1975);16-Arai, Nose &
Hashimoto (1975); 17-Sakamoto & Yone (1973); 18-Satoh et al.,(1983); 19-Gatlin et al., (1982); 20-Arai et al., (cited by Nose and Arai,
1979);21-Cowey et al., (1977); 22-Knox, Cowey & Adron (1981); 23-Ogino, Takashima &Chiou (1978); 24-Knox, Cowey & Adron (1983); 25-
Satoh et al., (1983a); 26-Sakamoto& Yone (1978a); 27-Sakamoto & Yone (1978); 28-Kawatsu (1972); 29-Gatlin& Wilson (1983); 30-Ogino &
Yang (1979); 31-Ogino & Yang (1978); 32-Wekell,Shearer & Houle (1983); 33-Ishak & Dollar (1968); 34-Ogino & Yang (1980);35-Yamamoto et
al., (1983); 36-Poston, Combs & Leibovitz (1976); 37-Lall (1979); 38-Gatlin & Wilson (1984a); 39-Woodall & LaRoche (1964); 40-NRC
(1983);41-Kanazawa, Teshima & Sasaki (1984); 42-Gatlin & Wilson (1986).

Despite the adequate presence of macro and trace elements in virtually all raw ingredients commonly
used for fish feeding (Tacon and De Silva, 1983), and the ability of fish and shrimp to absorb certain trace
elements from the surrounding water, mineral deficiencies may arise under intensive culture conditions
through:

 The absence of a specific macro or trace mineral premix within the diet (for details of specific
mineral premix formulations see NRC, 1983).

 Reduced mineral bioavailability through dietary imbalances. The availability and utilization of
dietary trace elements in fish or shrimp is dependent upon the dietary source and form of the
element ingested, the adequacy of stores within the body, interactions with other mineral elements
present in the gastro-intestinal tract and within the body tissues (antagonisms), and finally by
element interactions with other dietary ingredients or their metabolites (ie. vitamins, fibre and
phytic acid). For example, Table 13 shows the relative availabilities or apparent absorption
efficiency of various forms or sources of dietary phosphorus for three fish species.

Table 13. Availability of various sources of dietary phosphorus in fish 1

Phosphorus source Channel catfish Common carp Rainbow trout

(%) (%) (%)

Phosphates

Sodium phosphate, mono 90 94 98

Potassium phosphate, mono - 94 98

Calcium phosphate:

monobasic 94 94 94

dibasic 65 46 71

tribasic - 13 64
Fish meals

Fish meal, white - 0–18 66

Fish meal, brown - 24 74

Fish meal, anchovy 40 - -

Fish meal, menhaden 39 - -

Protein sources

Egg albumin 71 - -

Casein 90 97 90

Brewers yeast - 93 91

Plant products

Rice bran - 25 19

Wheat germ - 57 58

Wheat middlings 28 - -

Corn, ground 25 - -

Soybean meal, with hulls 50 - -

Soybean meal, dehulled 29–54 - -

Phytate 0 8–38 0–19

1
Source: NRC (1983)

For certain fish species the availability and absorption of phosphorus and other major elements (ie.
calcium) from fish meal and meat and bone meal is further complicated by the absence of an acid-
secreting stomach, which is essential for normal bone solubilization. For stomachless fish species soluble
monobasic inorganic salts or bioavailable organic salts must therefore be provided in the diet. Conversely,
within plant proteins a large proportion of phosphorus is present as organically bound phytates. Not only
is phytic acid phosphorus believed to be largely biologically unavailable, but phytic acid also has the
capacity to chelate other trace elements (iron, copper, zinc, cobalt, molybdenum) and by so doing may
render them biologically unavailable to the fish during digestion (Spinelli, 1980; Robinson and Wilson,
1985).

Under practical farming conditions mineral deficiency signs often arise from a dietary imbalance of
calcium; due to the antagonistic effect of excess dietary calcium on the absorption of phosphorus
(Nakamura, 1982) and the trace elements zinc, iron and manganese (Lall, 1979). For example, the
bioavailability of zinc, and to a lesser extent manganese within white fish meal has been found to be
much lower than that contained in brown fish meal (which has a much lower ash and calcium content;
Ketola, 1978; Watanabe, Takeuchi and Ogino, 1980). Thus in experimeental feeding trials with rainbow
trout, chum salmon and common carp fed on diets in which white fish meal was used without a trace
element supplement, overt trace element deficiency signs arise such as depressed growth, short body
dwarfism and cataracts (Watanabe, Takeuchi and Ogino, 1980; Satoh et al., 1983, 1983a; Yamamoto et al,
1983).

6.6.2 Mineral toxicity

A major hazard which may be associated with the use of dietary feed ingredients is the presence of
potentially toxic mineral elements such as the accumulative elements copper, lead, cadmium, mercury,
arsenic, fluorine, selenium, molybdenum and vanadium. For example, contamination with copper may
arise from products fermented within copper lined vessels (ie. brewery by-products), or within pig and
poultry excreta from the use of copper based growth stimulants or anti-fungal agents. Other feed
ingredients which may contain potentially toxic metal contaminants include: poultry manure (arsenic);
paper pulp waste (lead); fish meal (mercury, selenium, arsenic, cadmium, and lead); poultry by-product
meals (zinc); shellfish (zinc); seleniferous accumulating plants of the
genera Astragalus and Machaeranthera, or cereals grown in seleniferous soils (selenium); and Antartic
krill (fluorine).

Dietary toxicity signs which have been reported in fish and shrimp under controlled laboratory conditions
include:

Element Species Toxicity sign 1

Zinc Common carp (C. carpio) Reduced growth (dietary level above 300 mg/kg Zn; 1)

Reduced growth, feed efficiency and haematocrit (dietary level

Copper 2 Channel catfish (I. punctatus)
above 15 mg/kg;2)

Selenium Reduced growth and feed efficiency, high mortality (dietary levels
Rainbow trout (S. gairdneri)
above 13 mg/kg; 3,4); nephrocalcinosis (4,5)

Channel catfish (I. punctatus) Reduced growth (dietary levels above 15 mg/kg; 6)

Cadmium Rainbow trout (S. gairdneri) Scoliosis, hyperactivity (7–10)

Common carp (C. carpio)

Scoliosis, lordosis, black tail, anaemia, degeneration of caudal fin

Lead Rainbow trout (S. gairdneri)
(11)

Chromium Rainbow trout (S. gairdneri) Reduced growth and feed efficiency (12)

Iron Penaeids (P. japonicus) Reduced growth (dietary levels above

0.014%; 13)
1
1-Jeng and Sun (1981); 2-Murai, Andrews & Smith (1981); 3-Hilton, Hodson &Slinger (1980); 4-Hicks, Hilton & Ferguson (1984); 5-Hilton &
Hodson (1983);6-Gatlin & Wilson (1984a); 7-Koyama & Itazawa (1977); 8-Koyama & Itazawa (1977a);9-Koyama & Itazawa (1979); 10-Roch &
Maly (1979); 11-Johansson-Sjöbeck & Larsson(1979); 12-Tacon & Beveridge (1982); 13-Kanazawa, Teshima & Sasaki (1984)
2
Recent trials with channel catfish failed to demonstrate a deleterious effect of40 mg supplemental copper/kg diet on growth, feed efficiency or
blood chemistry(Gatlin and Wilson, 1986a). The absence of dietary copper toxicity has alsobeen reported for rainbow trout fed 150 mg
supplemental copper or 500 mg totaldietary copper (Knox, Cowey and Adron, 1982, 1984).

Sumber : http://www.fao.org/docrep/field/003/ab470e/ab470e06.htm
CHROMIUM

This page looks at some aspects of chromium

chemistry required for UK A level (and its
equivalents). It includes: reactions of chromium(III)
ions in solution (summarised from elsewhere on the
site); the interconversion of the various oxidation
states of chromium; the chromate(VI)-dichromate(VI)
equilibrium; and the use of dichromate(VI) ions as an
oxidising agent (including titrations).

The first part of this page is a summary of the

reactions of chromium(III) ions in solution. You will
find links to other pages where these reactions are
discussed in more detail.

You are very unlikely to need everything on this page.

Check your syllabus and past papers to find out
exactly what you need to know.

Reactions of chromium(III) ions in solution

The simplest ion that chromium forms in solution is

the hexaaquachromium(III) ion - [Cr(H2O)6]3+.

Note: If you aren't happy about complex ions (including the

way they are bonded and named), it would pay you to follow
this link and explore the first couple of pages in the
complex ions menu before you go on.

Use the BACK button on your browser to return to this page.

The acidity of the hexaaqua ions

In common with the other 3+ ions, the

hexaaquachromium(III) ion is fairly acidic - with a pH
for typical solutions in the 2 - 3 range.

The ion reacts with water molecules in the solution. A

hydrogen ion is lost from one of the ligand water
molecules:

The complex ion is acting as an acid by donating a

hydrogen ion to water molecules in the solution. The
water is, of course, acting as a base by accepting the
hydrogen ion.
Because of the confusing presence of water from two
different sources (the ligands and the solution), it is
easier to simplify this:

However, if you write it like this, remember that the

hydrogen ion isn't just falling off the complex ion. It is
being pulled off by a water molecule in the solution.
Whenever you write "H+(aq)" what you really mean is a
hydroxonium ion, H3O+.

Note: You will find the full reasons for the acidity of
hexaaqua ionsif you follow this link. You only need to read
the beginning of that page which concentrates on
explaining the acidity of the hexaaquairon(III) ion. What is
said applies equally to the chromium-containing ion.

Use the BACK button on your browser to return to this page.

Ligand exchange reactions involving chloride or

sulphate ions

The hexaaquachromium(III) ion is a "difficult to

describe" violet-blue-grey colour. However, when it is
produced during a reaction in a test tube, it is often
green.

We nearly always describe the green ion as being Cr3+

(aq) - implying the hexaaquachromium(III) ion. That's

actually an over-simplification.

What happens is that one or more of the ligand water

molecules get replaced by a negative ion in the
solution - typically sulphate or chloride.

Replacement of the water by sulphate ions

You can do this simply by warming some chromium(III)
sulphate solution.

One of the water molecules is replaced by a sulphate

ion. Notice the change in the charge on the ion. Two of
the positive charges are cancelled by the presence of
the two negative charges on the sulphate ion.

Replacement of the water by chloride ions

In the presence of chloride ions (for example with

chromium(III) chloride), the most commonly observed
colour is green. This happens when two of the water
molecules are replaced by chloride ions to give the
tetraaquadichlorochromium(III) ion - [Cr(H2O)4Cl2]+.

Once again, notice that replacing water molecules by

chloride ions changes the charge on the ion.

Note: You will find an extensive discussion of ligand

exchange reactions if you follow this link.

Use the BACK button on your browser to return to this page.

Reactions of hexaaquachromium(III) ions with

hydroxide ions

Hydroxide ions (from, say, sodium hydroxide solution)

remove hydrogen ions from the water ligands attached
to the chromium ion.

Once a hydrogen ion has been removed from three of

the water molecules, you are left with a complex with
no charge - a neutral complex. This is insoluble in
water and a precipitate is formed.

Note: The colour coding is to show that this isn't a ligand

exchange reaction. The oxygens which were originally
attached to the chromium are still attached in the neutral
complex.

But the process doesn't stop there. More hydrogen

ions are removed to give ions like [Cr(H2O)2(OH)4]- and
[Cr(OH)6]3-.

For example:

The precipitate redissolves because these ions are

soluble in water.

In the test-tube, the colour changes are:

Note: You will find the reactions between hexaaqua ions

and hydroxide ions discussed in detail if you follow this link.
 Use the BACK button on your browser to return to this page.

Reactions of hexaaquachromium(III) ions with

ammonia solution

The ammonia acts as both a base and a ligand. With a

small amount of ammonia, hydrogen ions are pulled
off the hexaaqua ion exactly as in the hydroxide ion
case to give the same neutral complex.

That precipitate dissolves to some extent if you add

an excess of ammonia (especially if it is
concentrated). The ammonia replaces water as a
ligand to give hexaamminechromium(III) ions.

Note: You might wonder why this second equation is given

starting from the original hexaaqua ion rather than the
neutral complex. Explaining why the precipitate redissolves
is quite complicated. You will find the explanation in full
(although by reference to the corresponding copper case)
on the page about the reactions between hexaaqua ions and
ammonia solution.

Use the BACK button on your browser to return to this page.

The colour changes are:

Reactions of hexaaquachromium(III) ions with
carbonate ions

If you add sodium carbonate solution to a solution of

hexaaquachromium(III) ions, you get exactly the same
precipitate as if you added sodium hydroxide solution
or ammonia solution.

This time, it is the carbonate ions which remove

hydrogen ions from the hexaaqua ion and produce the
neutral complex.

Depending on the proportions of carbonate ions to

hexaaqua ions, you will get either hydrogencarbonate
ions formed or carbon dioxide gas from the reaction
between the hydrogen ions and carbonate ions. The
more usually quoted equation shows the formation of
carbon dioxide.

Apart from the carbon dioxide, there is nothing new in

this reaction:
 Note: You will find the reactions between hexaaqua ions
and carbonate ions discussed in detail if you follow this link.

Use the BACK button on your browser to return to this page.

The oxidation of chromium(III) to chromium(VI)

An excess of sodium hydroxide solution is added to a

solution of the hexaaquachromium(III) ions to produce
a solution of green hexahydroxochromate(III) ions.

This is then oxidised by warming it with hydrogen

peroxide solution. You eventually get a bright yellow
solution containing chromate(VI) ions.
The equation for the oxidation stage is:

Note: Although it is still a complex ion, you don't write

square brackets around the chromate(VI) ion - any more
than you would around a sulphate or carbonate ion.

If you want to know how to work out this equation , follow

this link.

Use the BACK button on your browser to return to this page.

Some chromium(VI) chemistry

The chromate(VI)-dichromate(VI) equilibrium

You are probably more familiar with the orange

dichromate(VI) ion, Cr2O72-, than the yellow
chromate(VI) ion, CrO42-.

Changing between them is easy:

If you add dilute sulphuric acid to the yellow solution

it turns orange. If you add sodium hydroxide solution
to the orange solution it turns yellow.
 Note: If you had just produced the yellow chromate(VI) ions
by oxidising chromium(III) ions using hydrogen peroxide, you
can't convert them into dichromate(VI) ions without taking a
precaution first.

In the presence of acid, dichromate(VI) ions react with any

hydrogen peroxide which is left in the solution from the
original reaction. To prevent this, you heat the solution for
some time to decompose the hydrogen peroxide into water
and oxygen before adding the acid.

The equilibrium reaction at the heart of the

interconversion is:

If you add extra hydrogen ions to this, the equilibrium

shifts to the right. This is consistent with Le
Chatelier's Principle.

Note: If you aren't familiar with Le Chatelier's Principle, you

should follow this link and read the first part of that page
about the effect of concentration on position of equilibrium.
 Use the BACK button on your browser to return to this page.

If you add hydroxide ions, these react with the

hydrogen ions. The equilibrium tips to the left to
replace them.

Making potassium dichromate(VI) crystals

Potassium dichromate crystals can be made by a

combination of the reactions we've already looked at
on this page.

Starting from a source of chromium(III) ions such as

chromium(III) chloride solution:

You add potassium hydroxide solution to give first a

grey-green precipitate and then the dark green
solution containing [Cr(OH)6]3-ions. This is all
described in detail further up the page. Notice that
you have to use potassium hydroxide. If you used
sodium hydroxide, you would end up eventually
with sodium dichromate(VI).

Now you oxidise this solution by warming it with

hydrogen peroxide solution. The solution turns yellow
as potassium chromate(VI) is formed. This reaction is
also described further up the page.

All that is left is to convert the yellow potassium

chromate(VI) solution into orange potassium
dichromate(VI) solution. You may remember that that
is done by adding acid. This is described above if you
have forgotten.

Unfortunately there is a problem here. Potassium

dichromate will react with any excess hydrogen
peroxide to give initially an unstable deep blue
solution and it eventually gives the original
chromium(III) ions again! To get around this, you first
need to destroy any excess hydrogen peroxide.

This is done by boiling the solution. Hydrogen

peroxide decomposes on heating to give water and
oxygen. The solution is boiled until no more bubbles of
oxygen are produced. The solution is heated further to
concentrate it, and then concentrated ethanoic acid
is added to acidify it. Orange crystals of potassium
dichromate are formed on cooling.

The reduction of dichromate(VI) ions with zinc and an

acid

Dichromate(VI) ions (for example, in potassium

dichromate(VI) solution) can be reduced to
chromium(III) ions and then to chromium(II) ions using
zinc and either dilute sulphuric acid or hydrochloric
acid.

Hydrogen is produced from a side reaction between

the zinc and acid. This must be allowed to escape, but
you need to keep air out of the reaction. Oxygen in the
air rapidly re-oxidises chromium(II) to chromium(III).

An easy way of doing this is to put a bit of cotton wool

in the top of the flask (or test-tube) that you are using.
This allows the hydrogen to escape, but stops most of
the air getting in against the flow of the hydrogen.

The reason for the inverted commas around the

chromium(III) ion is that this is a simplification. The
exact nature of the complex ion will depend on which
acid you use in the reduction process. This has
already been discussed towards the top of the page.

Note: To re-read this use this link.

The equations for the two stages of the reaction are:

For the reduction from +6 to +3:

For the reduction from +3 to +2:

Note: If you don't know how to work out equations like this,
you can find out how to do it on the page about writing ionic
equations for redox reactions.

Use the BACK button on your browser to return to this page.

Using potassium dichromate(VI) as an oxidising agent
in organic chemistry

Potassium dichromate(VI) solution acidified with

dilute sulphuric acid is commonly used as an oxidising
agent in organic chemistry. It is a reasonably strong
oxidising agent without being so powerful that it
takes the whole of the organic molecule to pieces!
(Potassium manganate(VII) solution has some
tendency to do that.)

It is used to:

 oxidise secondary alcohols to ketones;

 oxidise primary alcohols to aldehydes;

 oxidise primary alcohols to carboxylic acids.

For example, with ethanol (a primary alcohol), you can

get either ethanal (an aldehyde) or ethanoic acid (a
carboxylic acid) depending on the conditions.

 If the alcohol is in excess, and you distil off the

aldehyde as soon as it is formed, you get ethanal
as the main product.

 If the oxidising agent is in excess, and you don't

allow the product to escape - for example, by
heating the mixture under reflux (heating the
flask with a condenser placed vertically in the
neck) - you get ethanoic acid.

In organic chemistry, these equations are often

simplified to concentrate on what is happening to the
organic molecules. For example, the last two could be
written:

The oxygen written in square brackets just means

"oxygen from an oxidising agent".

Note: These are not a proper substitute for real equations.

Only use them if your examiners are happy with them.
Check your syllabus and look at past papers and mark
schemes.

If you are working towards a UK-based exam and don't have

these things, you can find out how to get hold of them by
going to the syllabuses page.

Using this same reaction to make chrome alum

crystals

You will find chrome alum under all sorts of different

names:

 chrome alum

 potassium chromium(III) sulphate

 chromium(III) potassium sulphate

 chromium(III) potassium sulphate-12-water

 chromium(III) potassium sulphate

dodecahydrate

. . . and various others!

You will also find variations on its formula. For

example:

 CrK(SO4)2,12H2O

 Cr2(SO4)3,K2SO4,24H2O

 K2SO4,Cr2(SO4)3,24H2O

The first of these formulae is just the other ones

divided by two and rearranged a bit. Personally, I
prefer the second one because it is easier to
understand what is going on.

Chrome alum is known as a double salt. If you mix

solutions of potassium sulphate and chromium(III)
sulphate so that their molar concentrations are the
same, the solution behaves just like you would expect
of such a mixture. It gives the reactions of
chromium(III) ions, of potassium ions, and of sulphate
ions.

However, if you crystallise it, instead of getting mixed

crystals of potassium sulphate and chromium(III)
sulphate, the solution crystallises as single deep
purple crystals. These are "chrome alum".

Chrome alum crystals can be made by reducing

acidified potassium dichromate(VI) solution using
ethanol, and then crystallising the resulting solution.

Assuming you use an excess of ethanol, the main

organic product will be ethanal - and we've already
seen this equation above:

This ionic equation obviously doesn't contain the

spectator ions, potassium and sulphate. Feeding those
back in gives the full equation:
If you look at the top line on the right-hand side of the
equation, you will see that the chromium(III) sulphate
and potassium sulphate are produced in exactly the
right proportions to make the double salt.

What you do, then, is this:

Note: I am not giving quantities and exact conditions -

there are practical and safety considerations which make
me reluctant to do that. If you want precise details, they
aren't difficult to find.

You start with a solution of potassium dichromate(VI)

to which has been added some concentrated
sulphuric acid. The solution is then cooled by standing
it in ice.

An excess of ethanol is added slowly with stirring so

that the temperature doesn't rise too much.

Note: If the solution gets too warm, you get a ligand

exchange reaction between water molecules attached to
the chromium(III) ions produced and sulphate ions in the
solution. This leads to the green form of chromium(III)
sulphate described higher up the page. To make chrome
alum crystals, you have to stop this happening.

When all the ethanol has been added, the solution is

left over-night, preferably in a refrigerator, to
crystallise. The crystals can be separated from the
remaining solution, washed with a little pure water
and then dried with filter paper.
Using potassium dichromate(VI) as an oxidising agent
in titrations

Potassium dichromate(VI) is often used to estimate

the concentration of iron(II) ions in solution. It serves
as an alternative to using potassium manganate(VII)
solution.

Note: Potassium manganate(VII) titrations are described

fully on the page about manganese chemistry.

In practice

There are advantages and disadvantages in using

potassium dichromate(VI).

Advantages

 Potassium dichromate(VI) can be used as a

primary standard. That means that it can be
made up to give a stable solution of accurately
known concentration. That isn't true of
potassium manganate(VII).

 Potassium dichromate(VI) can be used in the

presence of chloride ions (as long as the
chloride ions aren't present in very high
concentration).

Potassium manganate(VII) oxidises chloride ions

to chlorine; potassium dichromate(VI) isn't quite
a strong enough oxidising agent to do this. That
means that you don't get unwanted side
reactions with the potassium dichromate(VI)
soution.

Disadvantage
  The main disadvantage lies in the colour change.
Potassium manganate(VII) titrations are self-
indicating. As you run the potassium
manganate(VII) solution into the reaction, the
solution becomes colourless. As soon as you add
as much as one drop too much, the solution
becomes pink - and you know you have reached
the end point.

Unfortunately potassium dichromate(VI) solution

turns green as you run it into the reaction, and
there is no way you could possibly detect the
colour change when you have one drop of excess
orange solution in a strongly coloured green
solution.

With potassium dichromate(VI) solution you have

to use a separate indicator, known as a redox
indicator. These change colour in the presence
of an oxidising agent.

There are several such indicators - such as

diphenylamine sulphonate. This gives a violet-
blue colour in the presence of excess potassium
dichromate(VI) solution. However, the colour is
made difficult by the strong green also present.
The end point of a potassium dichromate(VI)
titration isn't as easy to see as the end point of a
potassium manganate(VII) one.

The calculation

The half-equation for the dichromate(VI) ion is:

. . . and for the iron(II) ions is:

Combining these gives:

You can see that the reacting proportions are 1 mole

of dichromate(VI) ions to 6 moles of iron(II) ions.

Once you have established that, the titration

calculation is going to be just like any other one.

Note: If you aren't very good at doing titration calculations,

you might be interested in my chemistry calculations book.

Testing for chromate(VI) ions in solution

Typically, you would be looking at solutions containing

sodium, potassium or ammonium chromate(VI). Most
chromates are at best only slightly soluble; many we
would count as insoluble.

The bright yellow colour of a solution suggests that it

would be worth testing for chromate(VI) ions.

Testing by adding an acid

If you add some dilute sulphuric acid to a solution

containing chromate(VI) ions, the colour changes to
the familiar orange of dichromate(VI) ions.

You can't rely on this as a test for chromate(VI) ions,

however. It might be that you have a solution
containing an acid-base indicator which happens to
have the same colour change!

Testing by adding barium chloride (or nitrate) solution

Chromate(VI) ions will give a yellow precipitate of

barium chromate(VI).

Note: The precipitate colour is very

similar to the background colour I use on
Chemguide pages, which makes the last
diagram a bit difficult to see. The photo
on the right is by courtesy of Professor
Stanley G. Smith of the The University of
Illinois at Urbana-Champaign.

Testing by adding lead(II) nitrate solution

Chromate(VI) ions will give a bright yellow precipitate

of lead(II) chromate(VI). This is the original "chrome
yellow" paint pigment.