Xii - Chem - Vol-I - 2024-11-10T055508.444
Xii - Chem - Vol-I - 2024-11-10T055508.444
U N IT - I
Metallurgy
Evaluate yourself - 1
1 . W ri te th e eq uati on for th e ex trac ti on of si lver b y leac h i n g w i th sodi um c yan i de an d sh ow th at th e
leac h i n g p roc ess i s a redox reac ti on .
Role of NaCN in the extraction of silver (Ag) is to do the leaching of Ag ore in the presence of air from
which the silver is obtained later by replacement
4Ag + 8CN- + 2H2O +O2 4[Ag(CN)2] + 4OH- (Ag 0 Ag+ ) Oxidation reaction
both oxidation and reduction takes place, so it is show that the leaching process is a redox reaction.
Evaluate yourself - 2
2 . Mag n esi te ( Mag n esi um c arb on ate) i s c alc i n ed to ob tai n m ag n esi a, w h i c h i s used to m ak e refrac
tory b ri c k s. W ri te th e dec om p osi ti on reac ti on .
The decomposition temperature is given as 350 °C (662°F). However, calcination to the oxide is
generally not considered complete below 900 °C due to interfering readsorption of liberated CO2
MgCO3 MgO+ CO2
Evaluate yourself - 2
3 . U si n g Elli n g h am di ag ram i n di c ate th e low est tem p erature at w h i c h Z n O c an b e reduc ed to Z i n c
m etal b y c arb on . W ri te th e overall reduc ti on reac ti on at th i s tem p erature.
2 C O 2
-220 + O 2
2 C O
Go kJ mol
C + O 2
C O 2
- 410 2 C
O + O
2 Z n 2
-520 + O 2 C O
2 Z n
1000 K
T
By seeing the Ellingham diagram the free energy formation (Go) of CO from C becomes lower
temperature above 1120 K while that of CO2 from C becomes lower above 1323 K than (Go) of ZnO .
As (Go) of CO2 from CO is always higher than of ZnO. So C can reduce ZnO to Zn but not CO.Thus
carbon is better reducing agent than CO for ZnO
1) 1000K is the lowest temperature at which ZnO can be reduced to Zn.
2) The overall reaction for the following process is
Z n O ( s) + C ( s) Z n ( s) + C O ( g )
We can observe from the Ellingam diagram that the standard free energy change required for the
production of Carbon monoxide CO is less than the energy change required for the production of ZnO.
4 . Metalli c sodi um i s ex trac ted b y th e elec trolysi s of b ri n e ( aq . N aC l) . A fter elec trolysi s th e
elec trolyti c soluti on b ec om es b asi c i n n ature. W ri te th e p ossi b le elec trode reac ti on s.
H ook er c ell for elec trolysi s of brine (schematic). Since chloride ions are removed and hydroxide ions
produced by the electrolysis, the electrolyte gradually changes from a solution of sodium chloride to a
solution of sodium hydroxide.
Hooker cell for electrolysis
Three
✁✂✄☎✆✝✞✆ ✟✠✡✁ ✟✝☛☞✌ ✍✝✎✏✌ ✑☛
2
,H2,can be obtained by electrolyz ing an aqueous NaCl solution
(brine) 2H2O + 2e- H2+ 2OH -
Thus the overall reaction is : 2H2O(l) + 2Cl- aq H2 (g)+Cl2 (g) + 2OH- (aq)
The considerable effort required to concentrate the NaOH solution obtained from diaphragm cells
can be avoided by using mercury cells.
The cathode in such a cell is mercury, and the cathode reaction is
Na+(aq) + e- + xHg(l) NaHgx(l)
The sodium metal produced in this reaction dissolves in the liquid mercury, producing an amalgam.
The liquid amalgam is then transferred to an- other part of the cell and reacted with water:
UNIT- 2
p-Block Elements-I
Evaluate yourself : 1
Why group 18 elements are called inert gases? Write the general electronic configuraton of group
18 elements
The elements in group eighteen are Helium, Neon, Argon, Krypton, Xenon, and Radon.
These elements are all in all alluded to as noble gasses. The expression "noble gases" infers that
these elements have a tendency to be chemically inert or un- reactive.
electronic configuration of elements of group 18 is ns2 np6 with the exception of helium which has the
electronic configuration of 1s2.
D ue to the duplet or octet configuration in their valence shells, the group eighteen elements are
quite inert.
UNIT - 3
p-Block Elements - II
Evaluate yourself : 1
Write the products formed in the reaction of nitric acid (both dilute and concentrated) with zinc.
Zn reacts with dil.HNO3(20 to form nitrous oxide (N2O)
4Zn+10HNO3(dil.) 4Zn(NO3)2+N2O+5H2O
Zn+4HNO3(conc.) Zn(NO3)+2NO2+2H2O
UNIT- 4
Transition and Inner Transition Elements
Evaluate yourself: 1
Compare the stability of Ni4+ and Pt4+ from their ionisation enthalpy values.
IE Ni Pt
I 737 864
II 1753 1791
III 3395 2800
IV 5297 4150
Sum of four ionisation enthalpy of Ni is= I E1+I E2+I E3+ I E4 = 11,182 kJ
Sum of four ionisation enthalpy of P t is = I E1+I E2+I E3+ I E4 = 9,555 kJ
ii) However, the sum of the first four I E of Pt4+compounds is lower than that of the first 4 I Es of Ni4+
and is therefore relatively stable.
Pt4+compounds are more stable because the sum of first four ionisation enthalpy is less than that of Ni4+
Smaller the I onisation enthalpy greater will be the thermodynamic stability of its compounds
Evaluate yourself: 2
Why iron is more stable in +3 oxidation state than in +2 and the reverse is true for Manganese?
Mn2+ is more stable than Mn3+ due to the stable electronic configuration of Mn2+ because of half filled
d- orbital. Fe3+ is more stable than Fe2+ because Fe3+ has exactly half filled d- orbitals which give the
stability to Fe3+ while Fe2+ has 3d6 electronic configuration.
UNIT 5
Coordination Chemistry
Evaluate yourself 1:
When a coordination compound CrCl3.4H2O is mixed with silver nitrate solution, one mole of
silver chloride is precipitated per mole of the compound. There are no free solvent molecules in
that compound. Assign the secondary valence to the metal and write the structural formula of the
compound.
CrCl3.4H2O it gives one mole of AgCl , [Cr(H2O)4Cl2]Cl [Cr(H2O)4Cl2]+ + Cl -
Total two ions mean one ioniz able ion and one complex ion non ionisable.
primary valence of Cr is +3 and is satisfied by Cl- ions. The secondary valence of Chromium is 6
[Cr(H2O)4Cl2]Cl - (tetraaquadichloridocobalt (I I I ) chloride)
Evaluate yourself -2:
2. I n the complex, [P t(NO2) (H2O) (NH3)2 ] Br,identify the following
i. Central metal atom/ ion
ii. L igand(s) and their types
iii. Coordination entity
iv. Oxidation number of the central metal ion
v. Coordination number
Ans:
i. Central metal atom/ion - P t (I I )
ii. Ligand(s) and their types - unidentate ligands( NO2- nitrito, H2O - aqua, NH3 - ammine)
iii. Coordination entity - coordination entity is enclosed in square brackets [P t (NO2) (H2O) (NH3)2]+
iv. Oxidation number of the central metal ion is = +2 [ x + (- 1)1 + 1(0) + 2(0) = +1, x = +2]
v. Coordination number - 4
Evaluate yourself 3:
A. Write the IUPAC name for the following compounds.
i) K2[Fe(CN)3(Cl)2(NH3)] - P otassiumamminedichloridotricyanido- N- ferrate(I I I )
0.54
266.5g of A will loss = × 266.5 = 36 g
4
This weight of 36g shown that on dehydration A gives two moles H2O
( molecular mass of H2O)= 1 × 2 +16 = 18g )
i.e. two moles of H2O are present outside the coordination sphere in the composition of A
Thus the composition of A is given by compound A = [Cr(H2O)4CI2]CI.2H2O
ii) Compound B
0.5 g of B gives (0.5- .0.466) g = 0.034 g of H2O on dehydration
0.034
266.5g of B will loss = × 266.5 = 18.122
0.5
This weight of 18.122 g shown that on dehydration B gives one moles H2O
The weight (= 18.122g) corresponds to one mole of H2O Thus B has one H2O mole outside the coordina
tion sphere and hence the composition of B is give by compound B = [Cr(H2O)5CI] Cl2.H2O
ii) Compound C
Since C shows no loss in water content no H2O molecule is outside the coordination sphere and hence
the comosition of C is given by compound C = [Cr(H2O))6]CI3
6. Indicate the possible type of isomerism for the following complexes and draw their isomers
(i) [Co(en)3][Cr(CN)6] (ii) [Co(NH3)5(NO2)]2+ (iii) [Pt(NH3)3(NO2)]Cl
Evaluate yourself 8:
8. The spin only magnetic moment of Tetrachloridomanganate(II)ion is 5.9 BM. On the basis of VBT,
predict the type of hybridisation and geometry of the compound.
Mn (Z= 25) (3d5 4s2), Mn2+- 3d5 4s0
4d5 4s 4p
2- x x x x
[MnCl4] x x x x
Cl- Cl- Cl- Cl-
sp3 - hybridization
4d7 4s 4p
x x x x
x x x x
[CoCl4]2- Cl- Cl- Cl- Cl-
sp3 - hybridization
10. A metal complex having composition Co(en)2Cl2Br has been isolated in two forms A and B. (B)
reacted with silver nitrate to give a white precipitate readily soluble in ammonium hydroxide.
Whereas A gives a pale yellow precipitate. Write the formula of A and B. state the hybridization of
Co in each and calculate their spin only magnetic moment.
a) i) Compound A reacts with AgNO3 to give a white ppt readily soluble in dil. aq.NH3
ii) Compound B reacts with AgNO3 to give a pale yellow soluble precipitate in conc.NH3
= - 32800 cm-1 Larger negative CFSE value indicates that low spin complex is stable
12. Draw energy level diagram and indicate the number of electrons in each level for the complex
[Cu(H2O)6]2+. Whether the complex is paramagnetic or diamagnetic?
o>P
d orbitals will split in to two different energy level is t2g and eg.
The presence of one unpaired electron in the eg level , so [Cu(H2O)6]2+ complex is a paramagnetic
13. For the [CoF6]3- ion the mean pairing energy is found to be 21000 cm-1. The magnitude of
o is 13000 cm-1. Calculate the crystal field stabilization energy for this complex ion correspond
ing to low spin and high spin states✒
CFSE= { [n t2g (-0.4) + n eg (0.6)] o + npP} - {n’p P}
o
= splitting energy is 13000 cm-1 and pairing energy is 21000 cm-1
= 10800 cm-1
Larger negative CFSE value indicates that low spin complex is stable
UNIT - 6
Solid State
Evaluate yourself -1
1. An element has a face centered cubic unit cell with a length of 352.4 pm along an edge. The density of
-3
the element is 8.9 gcm . How many atoms are present in 100 g of an element?
Z ×M
ρ=
N × a3
A
= density Z = number of atom in unit cell
M = atomic mass NA = Avogadro's number
a = edge length of unit cell
Given data :
Density = 8.9 gcm-3
Number of atom in unit cell of FCC (Z) = 4
Edge length = 352.4 pm = 352.4 x 10 -10 cm ( 1 pm = 10-10 cm)
Avogadro's number ( NA) = 6.023 x 1023 mol-1
Mass of element = 100 g
2. Determine the density of CsCl which crystallizes in a bcc type structure with an edge
length 412.1 pm.
+ -
Strcuture of Cesium chloride is body centre cubic type in which Cs placed within centre and Cl placed
at corner of lattice.
number of Cl- ions per unit cell = 8 × 1/8 = 1
number of Cs+ ions per unit cell = 1
so, there is only one molecule of CsCl in a lattice .
molar mass of CsCl
so, mass of one molecule of CsCl =
Avogadro's number
(133 + 35.5)
= = 2.8 × 10 - 22 g
6.023 × 10²³
volume of lattice = a³ , where a is edge length
= (412.1 × 10x-12)³
= 7 × 10-23 cm³
so, density of CsCl crystal = 2.8 × 10-22/7 × 10-23 = 4 g/cm³
o
3. A face centered cubic solid of an element (atomic mass 60) has a cube edge of 4A .Calculate
its density
Unit-cell edge length =400 pm = 400×10-10cm
1 1
Number of atoms in the fcc unit cell = 8 × +6× =4
8 2
Atomic mass 60
Mass of one atom =
Avogadro's number 6.023 × 10²³
4 x 60
Mass of the unit cell =
6.023 × 10²³
1 1 [NO2 ]
- x 2.5 x 10- 4 = +
2 4 dt
[NO ] 4
i) 2 2 2.5 x 10- 2 = 5 10- 2 mol L-1 s-1
dt 2
1 [NO2 ] d[O ]
2 ,
ii)
2 dt dt
d[O ] 1
2 2.5 x 10- 2 1.25 10- 2 mol L-1 s-1
dt 2
Evaluate yourself 2
1) For a reaction, X + Y product ; quadrupling [x] , increases the rate by a factor of 8. Quadru
pling both [x] and [y], increases the rate by a factor of 16.Find the order of the reaction with
respect to x and y. what is the overall order of the reaction?
rate = k [X]a[Y]b ----------------- 1
3
order of X =
2
2). Find the individual and overall order of the following reaction using the given data.
y
7.8 x10-5 = k [0.1]X [0.1] .................... 1
y
3.12 x10-4 = k [0.2]X [0.1] ................... 2
y
9.36 x10-4 = k [0.2]X [0.3] . .................. 3
i) dividing (2) by (1)
y
3.12x10- 4 k [0.2]x [0.1] X
= x [0.1]y = 4 = 2 , x = 2
7.8x10 - 5 k [0.1]
y
9.36x10- 4 k [0.2]x [0.3]
y
1
= x y =3= 3 = (3-1)y y = -1
3.12x10- 4 k [0.2] [0.1] 3
The order with respect to NO is = 2
The order with respect to O is = -1
rate = k [NO]2[O2]–1
The over all order of the reaction = 2 - 1 = 1
Evaluate yourself: 3
(1) In a first order reaction A products 60% of the given sample of A decomposes in 40
min. what is the half life of the reaction?
2.303 a
k= log
t a-x
a = 100 ( initial concentration) t = 40 min x = 60%
2.303 100
k= log
40 100 - 60
0.9163
k = = 0.0229 min-1
40
0.693 0.693
t1 = 30.26 min
2 k 0.0229
(2) The rate constant for a first order reaction is 2.3 x10-4 s-1 . If the initial concentration of the
reactant is 0.01M . What concentration will remain after 1 hour?
2.303 [A o ]
k= log , k = 2.3 x 10-4 s-1 t = 1 hr = 60 x 60
t [A]
2.303 [0.01]
2.3 x10-4 = log
60 x 60 [A]
[0.01]
log =36 x10-2
[A]
[0.01]
log = 0.36
[A]
[0.01]
= antilog (0.36) = 2.29
[A]
0.01
[ A] = 4.4 x 10 3 M
2.29
The concentration will remain after 1 hour is = 4.4 x10-3 M
(3) Hydrolysis of an ester in an aqueous solution was studied by titrating the liberated carboxylic
acid against sodium hydroxide solution. The concentrations of the ester at different time
intervals are given below.
2.303 Vo
k= log
t Vt
190000
log 8 x 10-4 = log A
2.303 x 8.314 x 500
1900 1900
log 8 x 10-4 = log A log A
2.303 x 8.314 x 5 95.7357