Compounds of Copper:

Copper Sulphate (Blue Vitriol), CuSO4.5H2O:

Preparation:
(i) It is prepared by dissolving copper (ii) oxide or copper (ii) carbonate in dil. Sulphuric
acid.

CuO H 2 SO
4 4
CuSO H 2O

CuCO3 H 2 SO
4 4
CuSO CO2 H 2O

CuSO4 .5H 2O
On evaporation, solution is concentrated, blue crystals of separate out on
cooling.
(ii) On a large scale, copper (ii) sulphate is obtained by passing ait through a hot mixture

H 2 SO4
of copper and dil.

2Cu 4 H O
2 2
2Cu 2 H 2O

Properties:
CuSO4 .5H 2O
(i) On heating loses water molecules as follows.
373K
CuSO4 .5H 2O
Strong
CuSO 4 .H 2O 423K CuSO4 CuO SO3

CuSO4 6 NH 4OH Cu NH 3 4 OH 2 NH 4 2 SO4 4 H 2O

Schweitzer's reagent
(ii)
2CuSO4 4 KI Cu2 I 2 I 2 2 K 2 SO4
(iii)
A mixture f copper sulphate and lime, under the name of Bordeaux mixture is used as a
fungicide in agriculture.
Silver Nitrate, AgNO3 (Lunar Caustic):
Preparation: It is prepared by dissolving the metal in dilute nitric acid and crystallizing
the solution

3 Ag 4 HNO
3 3 2H
3 AgNO 2O NO

Properties:
(i) On heating, it gives metallic silver and nitrogen dioxide
450
2 AgNO
3 2 Ag 2 NO2 O2

(ii) It reacts with iodine in two ways.

 5 AgNO3 3l2 3H 2O 3 5Agl 5HNO3
HlO
(a) When iodine is in excess:
AgNO3
(b) When is in excess

6 AgNO3 3l2 3H 2O 3 5Agl 6HNO3

AglO

(iii) When treated with alkali, it gives precipitate of silver oxide, which dissolves in excess

NH 4OH
of

2 AgNO3 2 NaOH Ag2O 3

2 NaNO H 2O
brown ppt

2 AgNO3 2 NH 4OH 2O
Ag 2 NH 4 NO3 H 2O

Ag 2O 4 NH 4OH 2 Ag NH 3 2 OH 3H 2O

Cl

NH 4OH
(iv) It gives turbidity with tap water and turbidity is soluble in .

AgNO3 Cl
AgCl NO3
tap water Turbidity

AgCl 2 NH 4OH Ag NH 3 2 Cl 2 H 2O
soluble

X-ray diffraction

X
10) RAY STUDY OF CRYSTAL STRUCTURE BRAGG METHOD.

BRAGGS EQUATION X RAY DIFFRACTION STUDIES.

X
ray diffraction studies of crystal clearly reveal the internal structure of
crystals.
The exact pattern of arrangement of crystal components, size and shape of
the unit cell.
Electromagnetic radiation propagate in the form of waves in all directions. In
the propagation of waves along a direction, the maximum displacement
perpendicular to motion of the wave is known as amplitude of the wave.
2 E0 ( E0 Amplitude)
For constructive interference resultant amplitude is
For destructive interference resultant amplitude is zero
 The waves, if present in the same phase they undergo constructive
interference on the other had if the waves are not in phase, they undergo
destructive interference.
BRAGGS EQUATION:

W.L. Bragg and W.H. Bragg worked out and gave a mathematical relation to
X
determine inter atomic distance from ray diffraction pattern. This relation is
called the Braggs equation

n 2d sin

n
order of reflection

X
Wave length of rays

d
interplanar distance

angle of reflection

Order of n Braggs
reflection equation
valu
e
First order 1 2d sin

Second order 2 d sin

Third order 3 2
d sin
3

nth n 2
d sin
order n

'n'
As value increases value increases
X X
rays of definite wave length obtained form ray tube, passes through a
slit and falls on a known face of the crystal. The position of the crystal can be
read on a scale.
X
The intensity of the diffracted ray from the crystal is measured on a
photographic plate or an ionization chamber. The ionization chamber contain

CH 3 Br
vapours.
 The extent of ionization in the vapour is shown by the electrometer reading.

X
As the intensity of the diffacted rays increases, the degree of ionization
also increases
By changing the angle of incidence the extent of ionization at different angles
is recorded in the electrometer.
The crests of the graph, taken from electrometer reflect maximum diffraction.
The angles corresponding to the crests are noted from the graphs.
' ' 'd '
The angles are substituted for in Braggs equation and the values of
are calculated.
1 2
;: : 1: 707 :1.154.
NaCl 'd ' 2 3
Ex: - For crystal values are in the ratio of From this it
is confirmed that the crystal has F.C.C. systems.

Note: - Braggs method to be used large single crystals are necessary. The planes
of the crystal must be fully developed and easily identified.

Lipids

Lipids are compounds of biological origin related to fatty acids and include fats, oils
waxes and other related compounds. They are stored in the adipose tissue. Lipids are
hydrophobic in nature and dissolve easily in non-polar organic solvent such as
chloroform and diethylether.

Based on their chemical composition, lipids are classified as follows :

Simple lipids (Homolipids)

Simple lipids are alcohol esters of higher fatty acids. They are further classified
into two types.

(i) Neutral fats (glycerides) : - These are triesters of glycerol with long chain fatty acid.

H 2 C OH H 2 C O CO(CH 2 )n CH3
| |
HC OH HC O CO(CH 2 ) n CH 3
| |
3HOOC CH 2 n CH3
H 2 C OH
H 2 C O CO(CH 2 )n CH3

Triglyceride
 (Neutral fat)

O
||
CH 2 O C R
| O
| ||
CH O C R '
| O
| ||
CH 2 O C R ''
or can be represented by the general formula

The fatty acids forming the ester always have an even number of carbons and
may be saturated .e.g. tristearin and tripalmitin.

H 2 C OCOC 7 H 35 H 2 C OCOC15 H 31
| |
HC OCOC17 H 35 HC OCOC15 H 31
| |
H 2 C OCOC17 H 35 H 2 C OCOC15 H 31

tristearin tripalmitin

Or unsaturated e.g. triolein

H 2 C OCOC17 H 33
|
HC OCOC17 H 33
|
H 2 C OCOC17 H 33

triolein

The glycerides of saturated fatty acids are called fats and those of unsaturated
fatty acids are called oils. Now, according to the structure the three same acid groups,
it is called simple glycerides and if the acid groups are different, it is called mixed
oleo palmio stearin
glyceride e.g. .

H 2 C OCOC17 H33
|
HC OCOC15 H31
|
H 2 C OCOC17 H35

oleo palmito stearin

 In solid state the molecules of saturated fatty fit closely together due to their
zigzag tetrahedral structure. The cis-saturated acid chains (example C-9 in oleic acid,
C17 H33COOH
) have a bend at the double bond and do not fit closely resulting in the
lowering of the melting point of the fat.

(ii) Waxes

These are esters of long chain saturated and unsaturated fatty acids with long chain
C14 C36
monohydroxy alcohols. The fatty acids range between to and the alcohols
C16 C36
range from to . Most of the waxes are mixtures and have higher melting
points than the neutral fats.

Compound Lipids (Hetrolipids)

Lipids with additional group are called compound lipids. These include

(i) Phospholipids (phosphotides)

These contain additional groups e.g. a phosphoric acid, nitrogen containing bases
and other substituents. Phospolipid are indispensable structural components of cell
membranes and are also used as detergents to emulsify fat for transport within the
body.

(ii) Glyco lipids

These are esters of fatty acids with carbohydrates and may contain nitrogen but no
phosphorus.

Derived Lipids

These are the substance derived from simple and compound lipids y hydrolysis.
These include fatty acids, fatty alcohols, mono and diglycerides, steroids, terpenes
and carotenoids. These are sometimes present as waste products of metabolism.

Carboxylic acids :

The reactions that occur when dicarboxylic acids are heated, are unique indeed. These
depends on the carbon chain length separating the two COOH groups.

(i) Acids with 1-C or no-C chain undergo Decarboxylation. Oxalic acid and malonic acid
decarboxylate, when heated, to form monocarboxylic acids.
 O O
H C O O H + C O
H O C C O H 2
150
O x a lic a c id F o r m ic a c id

O O
H C O O H + CO
H O C C H 2 C O H 2
150
M a lo n ic a c id A c e tic a c id

(ii) Acids with 2-C and 3-C chains undergo Cyclodehydration. Succinic acid and glutaric
acid react by intramolecular dehydration to give cyclic anhydrides that have 5- and 6-
membered rings respectively.

O
C
H 2C C O O H H 2C
O + H 2O
H 2C C O O H 300 H 2C
C
O
S u c c in ic a c id S u c c in ic a n h y d r id e

(iii) Acids with 4-C and 5-C chains undergo Cyclization to Ketones. Adipic acid and
pimelic acid decarboxylate and cyclize to give cyclopentanone and cyclohexanone
respectively.

H 2
C
C H 2 C H 2 C O O H H 2C
C = O + C O 2 + H 2O
300 H 2C
C H 2 C H 2 C O O H C
A d ip ic a c id H 2
C y c lo p e n ta n o n e

H2 H2
H2 CC
CH2 CH2 CO OH
H2C C = O + CO2 + H2O
H2C 300
CH2 CH2 COOH CC
H2 H2 H2
Pimelic acid Cyclohexanone

(iv) Acids with 6-C or higher chain undergo Intermolecular Dehydration to form Linear
Polymers. The dicarboxylic acids having six-carbon chain react by intermolecular
dehydration when a linear polymer results.

O O O O O O O O

H O C ( C H 2) 6C O H + H O C ( C H 2) 6C O H H O C ( C H 2) 6C O C ( C H 2) 6 C O H
H 2O
S u b e ric a c id ( 2 m o le c u le s ) A d im e r

The reaction continues with n molecules to yield a linear polymer.

3.8 Oxalic Acid

Ethanedioc acid, HOOC COOH

It occurs as potassium hydrogen oxalate in the wood sorrel, rhubarb, and tomatoes. The
insoluble calcium oxalate is found in some stony deposits in kidneys and bladder in
human body.

(A) Preparation

(i) Oxalic acid is made industrially by heating sodium formate to 400C.

400
2HCOON a N aOOC COON
a H2
Sod formate Sod oxalate

The sodium oxalate thus formed is dissolved in water and calcium hydroxide
added to precipitate calcium oxalate. The solution is filtered and the filtrate treated
with calculated quantity of dilute sulphuric acid to liberate the oxalate acid.
+
C O O N a C O O
+ C a (O H )2 C a 2+ + 2N aO H

+
C O O N a C O O
S o d o x a la te C a lc iu m o x a la te

C O O C O O H
C a 2+ + + C aS O

H 2S O 4 4
C O O C O O H
C a lc iu m o x a la te O x a lic a c id

Calcium sulphate precipitates, and oxalic acid is crystallized from the filtrate as
the hydrate, (COOH)22H2O.

(ii) In the laboratory, oxalic acid is made by oxidation of sucrose or molasses with
concentrated nitric acid in the presence of vanadium pentoxide as catalyst.

C O O H
H N O 3 + 5 H 2O
C 12H 22O + 1 8 [O ] 6
11
V 2O 5 C O O H
O x a lic a c id

The CHOH CHOH units present in sucrose molecule are split out and oxidized
to oxalic acid.

(B) Properties

When crystallised from water, colourless prismatic crystals of oxalic acid dihydrate,
(COOH)22H2O, are obtained. The dihydrate melts at 101.5C, while the anhydrous
acid melts at 189.5C. The hydrated acid becomes anhydrous when carefully heated
to 150C. Oxalic acid is an active poison, depressing the central nervous system and
causing malfunction of kidneys.
 Oxalic acid molecule is made of two carboxyl groups in direct union. It gives all
the usual reactions of COOH group twice. Also, the acid gives some particular
reactions which involve the cleavage of the weakened linkage between the two
highly oxidized carbon atoms.

(i) Formation of Mono-and Di-derivatives. Oxalic acid is a much stronger acid than acetic
acid and readily forms two series of salts, esters, acid halides and amide.

+
CO O N a C O O C 2H 5 CO Cl
+ CO N H 2
CO O N a C O O C 2H 5 CO Cl
D iso d iu m D ie th y l O x a ly l CO N H 2
o x a la te o x a la te c h lo r id e O x a m id e

(ii) Action of Heat. When heated at 150C, it decarboxylates to give formic acid.

150
HOOC COOH
HCOOH CO 2
Oxalic acid Formic acid

(iii) Action with Glycerol. Oxalic acid reacts with glycerol to form formic acid or allyl
alcohol, depending upon experimental conditions.

(iv) Action with H2SO4. When heated concentrated sulphuric acid, it is decomposed to
give carbon dioxide, carbon monoxide and water.

Conc. H 2SO4
HOOC COOH CO 2 CO H 2O

Oxalic acid

(v) Oxidation. It is readily oxidized, for example with acidified potassium permanganate.

KMnO 4
HOOC COOH [O] 2CO 2 H2 O
H 2 SO 4

Oxalic acid