ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM

Inorganic Chemistry

Organic reagents in inorganic analysis

Advantages of organic reagents over inorganic reagents
i) They more specific than inorganic reagents under certain conditions like pH, temperature etc.
ii) They are highly sensitive i.e. they can detect small amount of anlayte
iii) The precipitate formed with organic reagents are insoluble in water, so that the degree of
separation is easier
iv) The precipitate formed with organic reagents have large size so they can be easily filterable
v) Organic reagents produces colour during reaction which is helpful in detecting end point or
particular ion present
vi) organic reagents produce compounds that are having little affinity for water and are dried of
easily at low temperatures

Important Organic reagents in inorganic estimations

EDTA (Ethylene diamine tetra acetic acid)
EDTA is hex dentate ligand and form chelating complex with metal dipositive metal ions
Its commercially available as sodium salt of EDTA
It is heavy molecule and readily soluble in water therefore it is more advantageous
It forms colour with metal ions when it forms complex

Structure of EDTA Structure of Metal EDTA complex

M = Mg2+ Ca2+ or Zn2+

EDTA in estimation of Ca, Mg, Zn

Disodium salt of diamine tetra acetic acid (EDTA) used in estimation of dipositive metal ions
like Ca, Mg, Zn by complexometric titration using Erio-chrome Black T as indicator (abbreviated as
H3D),

In this titration the solution containing Mg2+ or Ca2+ or Zn2+ is buffered with pH = 10 (NH4Cl-NH4OH
Buffer), a few drops of indicator Erio-chrome black T are added and solution is titrated with standard
solution of EDTAH2Na2. In this titration indicator ion form red metal complex with Mg2+ or Ca2+ or Zn2+

Metal – indicator complex ion [M2+D]- reacts with EDTA4- ion and forms metal-EDTA complex
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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

EDTA ions also forms a metal-EDTA complex with free Mg2+ or Ca2+ or Zn2+ ions (present in the
solution) that have not reacted with indictor ion D3- to form [M2+D]- complex
Thus, we see that free indicator ion D3- is obtained at the end point. The release of the free indicator
ion is marked by change in colour from red colour to blue colour

Gravimetric estimation of Ni2+ ions by dimethyl glyoxime (DMG)

Dimethyl glyoxime solution reacts with Ni2+ in ammoniacal medium and forms an insoluble
red chelate of bis- (dimethyl glyoximato) nickel(II) Ni(C4H7O2N2)2. Thus the formation of this chelate
can be used for identification of Ni2+

Gravimetric estimation of Mg2+ by Oxine (8-hydroxyquinoline)

It is bidentate ligand with O and N as donor atom it readily soluble in mineral acids and organic
solvents , it is yellow in colour which is due to formation of quinoid structure
It forms complex with metal ions like Mg2+ to form Mg(C9H6ON)2

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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

The quantitative estimation of the complex is carried out by drying the complex and weighing the
hydrated or anhydrous complex or complex is ignited to oxide and then weighed.

1,10 phenanthroline or o-phenanthroline

It is neutral symmetrical bidentate ligand in which two nitrogen atoms serves as donor atoms, it
forms complex with Fe2+ ion to give [Fe(Phen)3]2+ complex ion
Iron(II) reacts with 1,10-phenanthroline to form an orange-red complex [(C 12H8N2)3 Fe]2+. The colour
intensity is independent of the acidity in the pH range 2-9, and is stable for long periods. Iron(III) may be
reduced with hydroxylammonium chloride and the complex is measured at 515 nm (blue-green filter)
against a reagent blank.
Both iron(II) and iron(III) can be determined spectrophotometrically: the reddish-orange iron(II) complex
absorbs at 515 nm, and both the iron(II) and the yellow iron(III) complex have identical absorption at 396
nm,. The solution buffered to pH of 3.9 the reading at 396 nm gives the total iron and that at 515 nm the
iron(II).

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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

BIOINORGANIC CHEMISTRY

Classification of elements according to their action in the biological system

Elements

Essential Trace Non-essential Toxic

O, C, H, N, P I, Fe, Cu, Zn, Mn, Al, Sr, Ba, Sn etc Cd, Pb, Hg etc
Na, K, Mg, Cl, Co, Mo etc,
Ca, S etc.

Essential elements are absolutely essential or necessary for life processes.

Trace elements are also necessary for life processes.
Non-essential elements are not essential. If they are absent other elements may serve the same
function.
Toxic elements disturb the natural functions of the biological system

Role of sodium
The chemical symbol Na is derived from the Latin natrium or arabicnatrum, and the word
sodium comes from the Latin “sodanum” meaning headache remedy
i) Maintenance of body fluids in humans
ii) Functioning of neurons and transmission of nerve impulses
iii) Important component of the extracellular fluid
iv) Maintain a constant Osmotic pressure of the blood
High intake of sodium leads to
i) Hypernatremia (high salt plasma levels): It leads to Cardiovascular disorder
ii) Hypertension which is defined as having a resting systolic/diastolic blood pressure
in excess of 140/90 mm of mercury
Low sodium level (Hyponatraemia) leads to
i)Dysfunction of kidneys
ii)Damage to the body via osmotic imbalances
iii) Dehydration and muscle cramps

Role of Potassium
i) It is mostly present in intracellular fluid
ii) It is essential for nervous impulsion and muscle contraction
iii) it main blood osmotic pressure
iv) important in metabolic functions like protein biosynthesis
Low level of potassium leads to Hypokalaemia
i) Symptoms: Weakness of the muscles and Electrocardiogram (ECG) abnormalities.
ii) It results from reduced K intake caused by Gastrointestinal (GI) disturbance,
diarrhoea and vomiting. Increased use of diuretics: thiazides drugs.

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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

iii) Treatment: Oral administration of Pot. Chloride (10% aq. Solution)

excess of potassium leads to Hyperkalaemia
i) Normal range of K ion in blood plasma is 3.5-5.0 mmol/l. Hyperkalaemia is defined
when K ion conc. exceeds 6.5mmol/L
ii) Symptoms: Nausea, vomiting, ulcerations and ECG changes.
iii)Treatment: Calcium gluconate inj. i.v. which minimizes heart problems.
iv) Diuretics, Dialysis is the best option.

Na+/K+ pump
In order to maintain the cell potential, cells must keep a low concentration of
sodium ions and high levels of potassium ions within the cell (intracellular). Outside cells
(extracellular), there are high concentrations of sodium and low concentrations of
potassium, so diffusion occurs through ion channels in the plasma membrane. In order to
keep the appropriate concentrations, the sodium-potassium pump pumps sodium out and
potassium in through active transport.
The ionic transport conducted by sodium pump creates both an electrical and
chemical gradient across the plasma membrane. Enzyme, NaP+P-KP+P ATPase is the major
component of the NaP+P-KP+P pump, which is essential in creating membrane potential. This
intrinsic membrane protein consists of two components; a 100KD catalytic subunit and a
45KD associated glycoprotein, organized in to a αB 2B βB2B tetramer.

First of all the NaP+P-KP+P pump bound with ATP binds 3 intracellular NaP+P ions
(step a). This starts phosphorylation of an Asp residue leading to a conformational
change, which weakens NaP+ P binding and moves NaP+P out of the cell (step b). A
conformational change in the pump exposes the NaP+P ions to the outside, where they are
released. ATP is hydrolysed during this process with the release of ADP. Now in the changed
conformational state pump binds 2 extracellular KP+P ions (step c). Potassium binding leads

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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

to dephosphroylation and return to original conformation (step d). In this conformation ATP
binds and the pump reorients to release KP+P ions inside the cell (step e). The pump is ready
to go again.

CALCIUM

Calcium derives its name from the Latin word calxor calcis meaning “lime”
It is very essential element in the human body for;
i) Bone and teeth formation [Hydroxyapatite [Ca10(PO4)6(OH)2], a calcium-phosphate
complex]
ii) Neuronal and skeletal muscle activity
iii) Cardiac and secretory activity of the glands
iv) Cell division and growth
v) Coagulation of blood.
vi) Calcium concentration in plasma is controlled by hormones: Calcitriol for
absorption of Ca from GI tract (active form of Vitamin D), Parathyroid hormone
(demineralization of bones) and Calcitonin (it favours bone formation /calcification).
Optimum intake of Ca can prevent Chronic diseases. Earlier, Ca intake was 2000-
3000mg/day per adult, but now-a-days it has decreased to an average of
600mg/day.
Calcium deficiency causes
osteoporosis, hypertension and weight management. Osteoporosis is known to be
the major underlying cause on bone fractures in postmenopausal women.
Higher calcium intake of around 1200 mg/day resulted in a significant reduction of
the recurrence of kidney stones by around 50%.
It is believed that the restriction of calcium leads to an increase in absorption and
excretion of oxalate in the urine and therefore promotes the formation of calcium
oxalate stones.

Iron
i) Is an essential trace element for the human body.
It is classified in to heme and non-heme iron Heme refers to a porphyrin ring
encompassing the iron in an octahedral complex present in haemoglobin myoglobin and
cytochromes Non-heme designates either an iron sulphur centre in a protein or low
molecular weight iron complexes.
ii) Haemoglobin is the oxygen-transport metalloprotein in the red blood cells;
myoglobin facilitates the oxygen use and storage in the muscles; and cytochromes
transport electrons to oxygen in mitochondria, active form of iron in Haemoglobin
and myoglobin is Fe+2
iii) there are enzymes which are based on irons they are Protection against oxidants
and toxicants (catalase, peroxidases, cytochrome P450) Fixation of atmospheric
nitrogen (nitrogenase) Synthesis of nucleic acids and lipids (ribonucleotide reductase,
fatty acid desaturase).

Deficiency of IRON causes

i) Anaemia: Treatment: Ferrous sulphate, ferrous fumarate, ferrous gluconate.
ii) Genetic disorders also causes Anaemia:
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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

iii) Sickle cell anaemia

iv) Cooley’s anaemia (insufficient production of beta-chain)
v) Thalassaemia (genetic disorder in Hb-structure)
vi) Repeated regular blood transfusions is the treatment

Transport and storage of iron

In lower organisms siderophores are the iron storing molecule examples are
enterobactin and desferrichrome. In mammals, the task of transferring iron from dietary
sources to haemoglobin initially involves the absorption of Fe(II) after passage through the
stomach, followed by uptake into the blood in the form of the Fe(III)-containing
metalloproteins called transferrins. Iron is transported as transferrin to protein ‘storage
vessels’ until it is required for incorporation into haemoglobin. In mammals, iron is stored
mainly in the liver (typically 250–1400 ppm of Fe is present), bone marrow and spleen in the
form of ferritin, a water-soluble metalloprotein example Apoferritin.
Siderophores: Iron storage molecule in lower organisms such as bacteria.
Ferritin: Iron storage protein in mammals.
Transferrin: Iron transferring protein from liver to haemoglobin.

ZINC
The average human body contains around 2 g of Zn2+. Therefore, zinc (after iron) is
the second most abundant essential metal ion the human body
i) it is present in large number of essential enzymes like carboxy peptidase, carboxy
anhydrase
ii) zinc helps in proper formation of proteins
iii) zinc helps in healing the wounds and helps in hair growth etc.
vi) proper functioning of bones muscle etc.
Deficiency of zinc causes
i) Growth retardation: Dwarfism
ii) Hypogonadism and hypospermia
iii) skin lesions; Diarrhoea ; Anorexia
iv) Alopecia and Inhibition of sexual maturation
v) Immune system compromise
vi) Delayed wound healing, burns, ulcers
vii) Eye lesions, photophobia, dark adaptations
viii) Behavioural changes and congenital malformation in the off spring

Toxicity of metal ions

Mercury (Hg)
Mercury has no biological function
i) If Mercury vapours are inhaled, they are absorbed in lungs, dissolve in blood and
ultimately they are carried to brain. This causes irreversible damage to central
nervous system
ii) Hg brings about genetic changes
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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

iii) Monomethyl mercury [CH3Hg] and dimethyl mercury [(CH3)2Hg] produces nervous
disorder in marine animals
iv) contact with Hg produces nervousness, fear, inability to make decision,
heaviness, irritability, headache, pessimism, sleeplessness, falling teeth and
diarrhoea.
Antidotes for mercury poisoning are D-pencillamine (DPA) and its N- acetyl
derivative (NAPA), and unithiol

Lead (Pb)
Lead has no biological function
i) lead causes malformation of red blood cells produces the disease of anaemia
ii) lead damages organs like liver, kidney
iii) lead causes coagulation of proteins
iv) lead develops abnormalities in fertility and pregnancy
v) lead gets bound with cellular enzymes and disrupts the functioning of cells and
organs of muscular circulatory and nervous system
In case of lead poisoning, intravenous injection of Ca-Na2. EDTA is given to the
patient.

Arsenic (As)
It is essential ultra-trace element present in red algae, chicks and some mammals
including humans
i) It is deadly poisonous it combines with sulphur present in enzyme and original
activity of enzyme weakened
ii) Arsenic used as insecticides by farmers which kills the insects
iii) Arsenic containing drinking water causes severe damage to skin, liver, and
kidneys
iv) Deficiency of As in chicks results in depressed growth
Recommended chelating antidote for detoxification of As is 2,3 dimarcaptopropanol
(BAL), D-pencilliamine

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BIBI AHMADI KHATOON DEPT OF CHEMISTRY
Yuvaraja’s college
ORGANIC REAGENTS IN INORGANIC ANALYSIS V SEM
Inorganic Chemistry

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Yuvaraja’s college