Join Us
@google+: http://gplus.to/ChemicalEngineering
@facebook: https://www.facebook.com/AllAboutChemcalEngineering
@facebook: https://www.facebook.com/groups/10436265147/
@facebook: https://www.facebook.com/pages/EbooksChemical
Engineering/238197077030
P~9a~~
PHYSICAL
CHEMISTRY
» PRAGATI PRAKASHAN
© AuthorsPhysical Chemistry Vol. I
PRAGATI PRAKASHAN
Head Office: Educational Publishers
PRAGATI BHAWAN Edition 2010
240, W. K. Road, Meerut250 001
SMS/Ph. : (0121) 6544642, 6451644
Tele/Fax: (0121) 2640642, 2643636
ISBN9788183984966
Visit us at : www.pragatiprakashan.in
email: pragatiprakashan@gmail.com
Regd. Office:
New Market, Begum Bridge, Meerut250 001
Published by : K.K. Mittal for Pragati Prakashan, Laser Typesetting : Pragati Laser Type
Setters Pvt. Ltd., (Phone: 2661657) Meerut. Printed at: Arihant Electric Presss, Meerut.
CONTENTS
IIUlij'
MATHEMATICAL CONCEPTS AND COMPUTER 155
1. Logarithmic and Antilogarithmic Relations 1
2. Find out the values of the following 5
3. Differentiation with Examples 7
412. Numerical Problems 1113
13. Integration and give important formulae 13
1423. Numerical Problems 16
24. Terms Permutation and Combination with Examples 22
2441. Numerical Problems . 23
42. Probability Definition 29
4350. Numerical Problems 32
51. Logarithmic, Trigonometric Series 32
52. Maxima and Minima 33
5357. Numerical Problem 34
58. Functioning, Characteristics, Limitations 38
Computer Programing Flow Charts 49
Fortan, Cobol, Basic, Pascal 50
Operating System 51
Exercise 52
oMultiple Choice Questions 52
oFill in the Blanks 54
oTrue or False 54
111~lij"
GASEOUS STATE 5~102
IIn"j'"
CHEMICAL AND PHASE EQUILmRIUM 103171
I
Chemical Equilibrium I
1. Law of mass action and eqUilibrium constant 103
2. Short notes on the following : 104
(i) Work function (ii) Free energy
3. Thermodynamic derivation of law of mass action 108
4. Thermodynamic derivation of van't Hoff isotherm 109
5. Thermodynamlc··derivation of van't Hoff isochore or van't 111
Hoff equation
6. Thermodynamic derivation of Clapeyron equation and 114
ClausiusClapeyron equation
7. LeChatelierBraun principle and applications to different 118
equilibria
o Numerical Problems 122
IPhase Equilibrium I
1. Explanation and illustration of phase, component and degree 126
of freedom
2. Phase rule and its thermodynamic derivation 129
3. Explain: Can all four phases in a one component system 131
coexist in equilibrium?
4. Application of phase rule to water system 131
5. Application of phase rule to sulphur system 134
6. Short notes on : 137
(a) Nonvariant system in phase rule studies
(b) Triple point
(c) Transition point
7. Two component system, graphical representation, reduced 138
phase rule equation, condensed state
8. Application of phase rule to leadsilver system 140
9. Application of phase rul~ to potassium iodide and water 142
system
10. Determination of number of phases and components of 143
different systems
11. Calculation of degree of freedom 143
12. Determination of number of phases, components and degree 144
of freedom of different systems
13. Ideal solutions, vapour pressure of such solutions 144
14. Nonideal or real solutions, vapour pressure curves of 147
completely miscible binary solutions
15. Theory of fractional distillation of binary solutions 150
16. (a) Theory of partially miscible liquid pairs, e.g., 154
(i) Phenolwater system
Oi) Triethylamine water system
(x)
III~I'M
CHEMICAL KINETICS AND CATALYSIS 211276
I
Chemical Kinetics I
1. (a) Explain the terms: rate of chemical reaction, velocity 211
coefficient, molecularity and order of reaction
(b) Difference between molecularity and order of reaction
(c) Why reactions of higher orders are rare?
(d) Factors which affect reaction rates?
2. Zero order reaction, rate expression, characteristics. 215
3. Half order reaction, rate expression, characteristic 216
4. First order reaction, rate expression, characteristics, examples 217
5. (a) Pseudounimolecular reactions 219
(b) Study of kinetics of hydrolysis of methyl acetate
6. Half life period for a first order reaction 220
7. Second order reaction, rate expression, characteristics, 221
examples and study of kinetics
8. Half life period for a second order reaction 224
9. Third order reaction, rate expressions, characteristics and 225
examples
10. nth order reactions, rate equation and characteristic 227
11. Methods employed in determining the order of reaction 228
12. Energy of activation and temperature coefficient 230
13. Activation energy, potential energy barrier and Arrhenius law 233
14. Collision theory for unimolecular reactions 235
15. Mathematical treatment of transition state theory, comparison 236
with collision theory.
o Numerical Problems 242
ICatalysis I
1. Catalyst, catalysis, types and classification of catalysis. 251
characteristics of catalytic reactions
2. Notes on the following: 258
(a) Catalytic promoters
(b) Catalytic poisons
3. Theories of catalysis, industrial applications of catalysts 261
4. Enzyme catalysis, characteristics and examples of enzyme 265
catalysis, kinetics of enzyme catalysis
5. Note on acidbase catalysis 269
o Multiple Choiae Questions 270
o Fill in the Blanks 274
o True or False 275
o Log and Antilog Tables (i)(iv)
MATHEMATICAL CONCEPTS AND COMPUTER
MATHEMATICAL CONCEPTS
Problem 1: Expillin the logarithmic and antilogarithmic reilltions with
suitable examples.
[A] Index
Multiplication of equal terms: If the term x is multIplIed Il tImes,
then multiplication will be x n , i.e.,
x x x x x x x x ... n times = x"
Here x is called the base and n is called index.
[8] Laws of Index
m
and ~
tnII
x" X
[C] Logarithms
Definition: If ab = c; then exponent 'b' is called the logarithm of number
'c' to the base 'a' and is written as log.. c = b, e.g., J~ = 81 ~ logarithm of
81 to the base 3 is 4, i.e., log3 81 = 4.
Note: a b = c, is called the exponential form and loga c = b is called the
logarithmic form, i.e.,
(i) T3 = 0.125 (Exponential form)
log2 0.125 =3 (Logarithmic form)
1
(ii) log64 8 ="2 (Logarithmic form)
(64)112 = 8 (Exponential form)
Laws of Logarithms
[I] First Law (product law) :
The logarithm of a product is equal to the slim of logarithms of its
factors.
logo (m X 11) = log" III + log" /I
2 PHYSICAL CHEMISTRYI
Remember:
loga m
1 ;/:. loga m  loga n
oga Il
[III] Third Law (Power law) :
The logarithm of a power of a number is equal to the logarithm of
the number multiplied by the power.
loga (mt = n loga m
Jlr l/n
Corollary: Since vm = m
1Jr l/n 1
., lo~ vm =lo&m =Io~m
n
Note:
(a) Logarithms to the base 10 are known as common logarithms.
(b) If no base is given, the base is always taken as 10.
(c) Logarithm of a number to the same base is always one, i.e.,
loga a = 1; 10glO 10 = 1 and so on.
(d) The logarithm of 1 to any base is zero, i.e.,
loga 1 = 0; logs 1 = 0; 10glO 1 =0 and so on.
(e) 10gJO 1 = 0; 10gJO 10 = 1;
10gIO 100 = 2
0 1 2 3 4 5 6 7 8 9 1 23 456 789
30 4771 4786 4800 4814 4829 4843 4857 4871 4886 4900 134 678 JO 11 13
31 4914 4928 4942 4955 4969 4983 4997 5011 5024 5038 1 34 678 JO 11 12
32 5051 5065 5079 5092 5105 5119 5132 5145 5159 5172 134 678 9 11 12
[E] Antilogarithms
If log 5274 = 3.7221, then 5274 is called the antilogarithm of 3.722l.
We write, antilog 3.7221 = 5274.
To find an antilogarithm, the antilogarithm tables are used.
The antilogarithm tables are used in the same way as the logarithm
tables. The only difference between the two tables is that the column at the
extreme left of the log table contains all two digit numbers starting from 10
to 99; whereas an antilog table contains numbers from .00 to .99 (i.e., all
fractional numbers with only two digits after decimal) in the extreme left
column of it.
x 0 1 2 3 4 5 6 7 8 9 123 456 789
0.35 2239 2244 2249 2254 2259 2265 2270 2275 2280 2286 1 1 2 233 445
0.36 2291 2296 2301 2307 2312 2317 2323 2328 2333 2339 1 12 233 445
037 2344 2350 2355 2360 2366 2371 2377 2382 2388 2393 I 12 234 455
0.38 2399 2404 2410 2415 2421 2427 2432 2438 2443 2449 1 1 2 234 455
[Note :
(i) Antilog tables are used only to find the antilogarithm of decimal
part.
(ii) To find the antilog of 2.368 means to find the number whose log
is 2.368].
Ex. 1 : If log x = 2.368,jind x.
Solution : log x = 2.368
x = antilog 2.368
Antilog 2.368 = the number characteristic of whose log is 2 and mantissa
is 368.
From antilog table, the value of .36 under 8 is 2333.
Since the characteristic of log of the number is 2.
:. The number has 2 + 1 =3 digits in its integral part (i.e., 3 digits before
the decimal point).
Antilog 2.368 = 233.3.
Ex. 2 : Find the antilog of 2.3536
Solution: From the antilog table, find the value of .35 under 3 and add
to it the mean difference under 6. The number thus obtained is 2257.
Now place the decimal point so that the characteristic of its log is 2.
.. Antilog 2.3536 = 0.02257
[Note:
(i) Antilog 0.5362 = 3.438 Antilog 1.5362 = 0.3438
(ii) Antilog 2.5362 = 343.8 Antilog 1.5362 = 0.003438
(iii) Antilog 4.5362 = 34380 Antilog 5.5362 = 0.00003438 and so on].
MATHEMATICAL CONCEPTS AND COMPUTER 7
d 1
(6)  (log x) =
dx e x
For example, differential coefficient of log (x + 1)
d [log (x + 1)] _1_. 1 = _1_
dx x+1 x+l
d 1
(7)  (log x) =  log e
dx a X a
For example, differential coefficient of log2 x, i.e.,
d 1
 (log x) =log~ e
d'( 2 X 
(l) dx
d (SIn
. x) = cos x (2) ~ (cos x) =  sinx
d ~ d 2
(3) dx (tan x) = sec x (4) dx (cot x) = cosec x
d d
(5) d (sec x) = sec x tan x (6) dx (cosec x) =  cosec x cotx
x
(7) ~ (sin mx) = m cos mx (8) ~ (cos I1lx) =  m sin mx
d 2
(9) d (tan IIlx) = 111 sec mx
x
[IV] Differentials of Inverse Functions
(1) dd (sinI x) =
x
bIx dx
x =  1 
(2) d (cosI)
{l=7
(3) dd (tanI x) = _1_ry (4 ) d (cotI)
x =   1 ,
x 1+x dx 1 +x~
d (I 1 d ( _) 1
(5) d sec x) = _~ (6) d cosec x = _~
x x'lx  1 x x 'IX  1
=x.e'+ex.l
l
=e (x+1)
MATHEMATICAL CONCEPTS AND COMPUTER 9
ou.) (OV)
~; =;y (~)= v ay ~ u ay
(
and
O I·ftierenttatmg
. . w.r.t. x. 1 ; = Iog y az
Z aX
az = z Iog y= yx Iog y
ax
Now differentiate equation (i), w.r.t y, we get
;~~=x(~)=~
or az (X)
ay=Z y =yx(X)
y =xy xI
...) dx
(III d (2. d (.
x sm x ) ::: X .z dx sm x ) + di
d (2).
x . sm x = "'='
~ SInX
12 PHYSICAL CHEMISTRYI
=
i cos x  sin x . 2.x
X4
X cos X  2 sin x
= 2
x
d
2 d 2
(x+l) ;t;;(x)x.;t;;(x+l)
••)  d [
(II X
dx (x + 1)2 (x+ 1)4
_ (x+ 1)2. Ix. 2. (x+ 1)
 (x+l)4
_ (x+ 1) [x+ 12.x] _ (Ix)
 (x+l)4 (x+l)3
Problem 9. Differentiate the following with respect to x :
(i) sin 5x (ii) log sin x (iii) (3x 2 + Il (Meerut 2007)
Solution.
(i) Let y = sin 5x => y = sin t, where t =5x
.. ~=cost
and dt =5
dx
dv dv dt
d; = di .dx = cos t . 5 = 5 cos 5x.
4r = 4r. dt = 1 . cos x
dx dtdx t
or 4r =_._1_ . cos x = cot x
dx smx
(iii) 1 (3x 2 2
+ 1)2 = 2 (3x + 1)21 . (6x)
= 2 (3x2 + 1) + (6x)
=12x (3x2 + 1)
MATHEMATICAL CONCEPTS AND COMPUTER 13
or !:!l. =  cott
dx
dy _ '2
.. dx  1 +x2"
Problem 12. If y =:
d .
tan1 (Sin x + C?S x) then calculate the value of f!:1...dx
cos x  SID X
. x~
SoIu tion. Let y = tan I (sin x + cos
cosx smx
represented by a symbol f.
If differential coefficient of f(x) is <I>(x), i.e.,
d
 [((x)] = <I>
dx
Therefore, f <I>(x) dx
14 PHYSICAL CHEMISTRYI
n :n;:, (n;t  1)
(4) Jx dx:%
(6) J ~dx=IOgeX
x
(7) f C dx=e
(8)faXdx=~
loge a
2
(15) J cos x dx = t +t
x sin x cos x + C
2
(16) Jsec x dx = tan x + C
MATHEMATICAL CONCEPTS AND COMPUTER 15
2
(18) ftan x dx = tan x  x + C
2
(19) fcot xdx=cotxx+C
(22) f ~1 ~X2 l
dx=sin x=cos x
l
(23) f~
l+x
dx = tan
l
x =  coe x
l
(25) f~=.!tanl~+
2 2
C
x +a a a
(26)
J dx
~=2
x a
1
1
ax
a
2
xa 2
loge+C,x >a
2
x+a
2
(27) Ih= a x
sin
1
~a + C, a > 0
[III] Definite Integral
When any functionf(x) is integrated between the lower limit and upper
limit of x, then it is called the definite integral.
For f(x), if the lower and upper limits of x are a and b, respectively,
then
f
a
b
1 [(3)6 
(2)6] = 729  64 = 665
=
6
Problem 14. Evaluate the following integrals:
(i) f X7 dx (li) f eX dx
f
7+ 1 8
S~lution. (i)
7
x dx =; + 1 =~
(ii) f eX dx = eX
(i) f 3
(x + 2x + 7) dx(ii) f (x
3
 2)2 dx
Solution. (i) f 3
(x + 2x + 7) dx = f f f
4
3
x dx +
2
2x dx +
4
7 dx
=£+~+7x=£+i+7x
4 2 4
(ii) f (x
3
 2)2 dx = f 6
(x + 4  4x ) dx
3
= f f f 6
x dx + 4 dx  4x dx
3
x7 4x3+ 1
=+4x
7 3+1
x7 4X4
=+4x
7 4
7
= ~+4xx4
7
·
So Iubon. (.)
I
f~!1
.
SIO X

 f (1

(l. + sin x) dx
. X )
sm x). (1 + Sin
MATHEMATICAL CONCEPTS AND COMPUTER 17
= f( 1 + sin x) dx
1  sin 2 x
=f(l+Si~X)dX
cos x
= f[ cos1 x2+~
sin x ]
cos x
dx
= f sec
2
x dx + f tan x . !>ec x dx
=tanx+secx
3
X 1
=x+tan x
3
f

(sec x + tanx)2
sec 2 x  tan 2 x
dx
18 PHYSICAL CHEMISTRYI
= I 2
see 2 x + (see xI) + 2 sec x tan x dx
= I 2
2 see x dx  I I I . dx + 2 sec x tan x dx
=2 f 2
f
see x dx  fl. dx + 2 sec x tan x dx
=2tanxx+2secx
Problem 19. Evaluate the following integrals by substitution method:
or dx= dt
a
I 7
(ax+b) dx= I7 II7
dt
t ;=~ t dt
=~(~)
1 8
= 8a (ax + b)
adx=dt or dx=dt
a
MATHEMATICAL CONCEPTS AND COMPUTER 19
=a1SIn.t 1
=a .SIn(ax + b)
Problem 20. Evaluate the /oUowing integrals:
(i) f~dx
eX + 1
(ii) f log x dx
x
(iii) f eX 2x dx
l+e
= log (eX + 1)
e
ldx=dt
x
f IO! =f
x dx t dt = ~
~
2
(iii) In f41 +e r
dx, put eX =t
f _e_tdx=f~=tanI
l+x2x 1+t2
t
=tan I e'.
20 PHYSICAL CHEMISTRYI
2
2x+3 dx= fdt
= log t
f x + 3x + 2 t e
= log e (x 2 + 3x + 2)
1
(ii) Put log x = t or  dx =dt
x
f 1
dx=
x log x
f dt
=log
t e
t
= loge (log x)
Problem 22. Evaluate the following integrals:
= log x f dx  f { ~ (log x) f dx } dx
= x log x  f ~ .x dx
=xlogx f dx
(ii) f x
xe dx = x f f{~ f
eX dx  (x) . eX dx } dx
MATHEMATICAL CONCEPTS AND COMPUTER 21
= xe'  fl. eX dx
= eX (x  1)
x2 1x
2
=Iogx
2 2 2
2 1
=~ (logX
2)
i
= 4 (2 log xI)
=  x COSJ + sin x
Problem 23. Evaluate the integral eX sin x dx.
= sin xf f{fx f
eX dx  (sin x) eX dx } dx
\. f
= e' sm x  cos x . e''dx
22 PHYSICAL CHEMISTRYI
or I = eX sin x  eX cos x  I
or 21 = eX sin x  e'\ cos x
1= t eX (sin x cos x)
Problem 24: Explain the terms permutation and combination with suit
able examples.
[I] Permutation
The number of different arrangements which can b~ made by Taking one
til1le some or all elements of any set of things, thell such every arrangement
is called a permutation.
Example: If in the set {a, b, c}, we take two elements in one time,
then the different arrangements which can be made are
ab,ba,bc,cb,ca,ac
Therefore, it is clear that the number of arrangements which can be
made by taking any two things at one time out of three things will be six.
[II] Principle of Permutation
If one work can be done in m ways and second work in n ways, then
both the works can be done together in m X n ways.
Important Formulae: The number of arrangements of taking r things
out of II different things is
"P r = n (11  1) (n  2) ...... (11  r + 1)
Factorial n :
II! = n (II  1) (n  2) ... 3.2.1
Here n ! is read as factorial Il and this is also represented by 1lL
Clearly, if r < 11
"Pr=n!
Important Results :
(l)nCn =1
II! = 0;n' or O! = 1.
So Iuti· on. 6p
3
6!
= (6 _ 3)1 = 3!
6! 6. 5 .4 . 3! 6 5 4 120
3! =.. = .
Problem 27. Prove that nPr = n x n lpr _ 1•
. S  n I _ n (n  1) !
So Iutlon. R.H ..  n x Pr  1  [n _ 1 _ (r  1)] !
n!
,
II. ="p =LHS
(n  1  r + I)! (II  r) ! r ...
Problem 28. Three persons enter into a car offive seats. In how many ways
can they occupy their seats?
24 PHYSICAL CHEMISTRYI
Solution. First person can sit in five ways as all the five seats are lying
vacant at the time of his entrance. The second person can sit on anyone of
the remaining four seats (one is already filled by first person). So. the second
person can sit in 4 different ways. Similarly, thIrd person can SIt in 3 different
ways on anyone of the three vacant seats (two already filled). Hence. all the
three can sit in 5 X 4 x 3 = 60 different ways.
Problem 29. (i) How many words can be formed with the letters of the
word "DELHI"?
(ii) How many of these will begin with D?
(iii) How many of these will end at D?
(iv) How many of these will begin with D or L?
(v) How many of these will begin with D and end at L?
(vi) How many of these will begin with D or end at L?
(vii) How mallY of the vowels "E, I" occupy the even number of
places?
(viii) How many of these will end at vowel only?
(ix) III how many of these vowels come together?
(x) How many of these will begin and end at vowel?
(xi) How many of these will begin and end with D or L?
Solution. (i) There are five letters "D, E, L, H, I" in the word DELHI.
These five letters can be rcalTanged among themselves in 5 ! ::; 120 ways, (or
say 5P s• i.e., the number of permutations of these five letters taking allthe
five at a time). Hence, we can form 120 different words.
(ii) All the arrangements in which D is 'in the beginning can be obtained
by fixing 'D' at the first place and then rearranging the remaining four letters.
Remaining four letters can be arranged in 4 ! ways. Hence, in 4 ! = 24 ar
rangements the words will begin with D.
Alternatively. First place can be filled by Din 1 way only, the second
place in 4 ways as any of the letters L. H, E, I can be put there; 3rd place can
be filled in 3 ways, 4th place in 2 ways and 5th place in one way only. Hence,
all the five can be filled in 1 x 4 x 3 x 2 x 1 = 4 ! = 24 ways.
(iii) The problem is similar to problem (ii) except that now we fix the
letter D on the last place. Hence, the remaining four letters can be arranged
in 4 ! ways. Hence, the required numb~r of words, ending at D, is 4 ! = 24.
(iv) As above there will be 4 ! arrangements starting with D, and also
4 ! an'angements will begin with L. Hence, the total number of arrangements
beginning with D or L are 4 ! + 4 ! = 48.
AlternaHvely. First place can be filled in two ways as any of the letters
D or L can be put there. Then second place can be filled in 4 ways as anyone
of the remaining fOur letters can be put there. The third place can be filled in
three ways. fourth place in two ways and fifth place can be filled in one way
only. Hence, all the five places can be filled in 2 x 4 x 3 x 2 x 1 = 48 ways.
MATHEMATICAL CONCEPTS AND COMPUTER 25
(v) In this we fix D at the beginning and L at the end. The remaining
three letters E, H, I can be rearranged in 3 ! ways. Hence, 3 ! = 6 arrangements
will begin with D and end at L.
(vi) The arrangements which begin with Dare 4 ! and which end at L
are also 4 !. Hence total number of arrangements which begin with D or end
at L are 4 ! + 4 ! = 48.
(vii) There are only two even places namely 2nd. 4th. E and I can be
rearranged on these places in 2! ways. Further. remaining three letters
D, L, H can be put on 1st, 3rd and 5th places in 3 ! ways. Hence. the total
number of arrangements in which E, I occur at even places only, is
2 ! x 3! = 12.
(viii) The arrangements ending at E or I give the arrangements ending
at vowels. Such arrangements are 4 ! + 4 ! = 48. Proceed as in (iv).
(ix) We consider the two vowels forming as one letter say (E I). Thus
there are four letters D, L, H, (E I). These can be rearranged in 4 ! ways.
Further, two vowels E, I can be rearranged among themselves in 2 ! ways.
Hence, total number of arrangements in which vowels come together is
2 ! x4! =48.
(x) We want to put E or I in the beginning and at the end. For the 3 !
arrangements will begin with E and end at I. Again 3 ! arrangements will
begin with I and end at E. Hence, the number of required ways are
3 ! + 3 ! = 12.
(xi) As above the required number of ways is 12 (only letters E and I
are replac~d by D and L).
Problem 30. How mallY words call be formed from the letters of the word
'DAUGHTER' so that the vowels always come together? (Meerut 2006)
Solution: We consider three vowels forming as one letter say (AUE).
So, there are six letters DGHTR(AUE). These can be arranged in 6! ways.
Further three vowels, A, U. E. can be rearanged among thermselves in 3!
ways. So, total number of arrangements in which vowels come together is 6!
x 31 = 4320 ways.
Problem 31. How mallY words call beformed with the letters of the word
"MEERUT"? In how many of these words vowels occupy only even places?
Solution: (i) There are 6 letters in the word "MEERUT", and the letter
E is repeated 2 times in this word. Therefore, the total number of words that
can be formed with the letters of the word "MEERUT"
_ 6! _ 6 x 5 x 4 x 3 x (2!)
 2!  2!
=6 x 5 x 4 x 3 =360
(ii) There are three even places in the word "MEERUT", namely,
second. fourth and sixth places, respectively. At these places the vowels
E, E and U are to be arranged. So, the number of ways to arrange
E, E and U at these three places
26 PHYSICAL CHEMISTRYI
= 3! =3
2!
Now at the odd places, the letters M, R, T are to be arranged; so the
number of ways to arrange M, R, T at three odd places
=3! =6
Thus, the total number of words in which the vowels occupy even places
=3 x6= 18.
Problem 32. How many permutations can be made out of the letters of
the word "BUSINESS"? How many ofthese will begin with B and end with
N?
Solution: (i) There are 8 letters in the word "BUSINESS", and the
letter S is repeated 3 times and others are different. Then the total number of
words formed by the letters of the word "BUSINESS" are
8!
 3!
=8x7x6x5x4=6720
(ii) If each word begins with letter B and ends with N, then except these
two letters, the remaining letters are 6 and out of 6 the letter S is repeated 3
times.
Now in this case, the total words formed by the letters of word
"BUSINESS" which begin with B and end with N are
=~=6
6' x 5 x 4 = 120
3!
Problem 33. Prove that nCr = nCn _ r
n!
(Il  r) ! (II  II + r) !
n!
(n  r) ! r!
= nCr = L.H.S.
Problem 34. Find the value of the following 24 C4 .
Solution.
24 24!
C4 = 4 ! (24  4) !
[ .,'
nC _
r
n.,
r! (n  r) !
]
24 !
4! 20!
_ 24 x 23 x 22 x 21 x (20!)
 4 x 3 x 2 x I x (20!)
24 x 23 x 22 x 21
4x3x2xl
MATHEMATICAL CONCEPTS AND COMPUTER 27
= 6 x 23 x 11 x 7
= 10626
Problem 35. Find the value ofr if20Cr _ 1 = 20Cr + l'
Solution. Since. we know that if nCx = nCy. then either x = y or x + y = n
Here. 2OCr _ I = 20Cr + I and r  1 "* r + 1
So. r+ 1 + r 1 = 20 (":x+y=n)
=> 2r=20
=> r=lO
Problem 36. In how many ways can a cricket eleven be chosen out of 15
players? How many of them will always (i) include a particular player? (ii)
exclude a particular player?
Solution. Number of ways of selecting cricket eleven
= Number of ways of selecting 11 players out of 15
= lSC = ~ = 15 . 14 . 13 . 12 . 11! = 1365
11 11! 4! 11! 4. 3. 1 .
(i) Now since a player is to be included always. we are to select
remaining 10 players out of the rest 14 players. This can be done in
14CIO = 1001 ways.
(ii) Again since a player is never to be included. i.e .• always excluded.
we are selecting 11 players out of 14 only. This can be done in IO ClI = 364
ways.
Problem 37. How many triangles can be made by joining 12 points in a
plane, given that 7 are in one line?
Solution. The triangles can be formed by joining any three points. But
7 points are in one line. Hence. with three points out of these 7 points in one
line. we cannot form a triangle. Hence. the required number of triangles is
12C3  7 C 3 = 185.
Alternative. Triangles can be formed in the following ways :
(i) Three points are taken from the five noncollinear points. Number
of ways is 5C3 = 10.
(ii) One point is taken from 5 noncollinear and 2 out of 7 collinear
points. This can be done in SCI x 7C2 ways = 105 ways.
(iii) Two points are taken from 5 noncollinear and 1 from 7 collinear
points. This can be done in sC2 x 7C1 ways = 70 ways.
Therefore. the required number of triangles = 10 + 105 + 70 = 185.
(Note that possibilities (i). (ii) are (iii) are mutually exclusive.)
Problem 38. Find the number of diagonals that can be drawn by joining
angular points. of a sixteen sided figure?
Solution. In a sixteen sided figure there will be 16 angular points
(vertices).
28 PHYSICAL CHEMISTRYI
Total number of lines which can be drawn by joining any two angular
points = 16 C2 = 120.
But out of these lines, 16 will be sides. Hence. the required number of
diagonals = 120  16 = 104.
Problem 39. In how many ways can 12 things be divided equally among
4 persons?
Solution: 12 things are divided equally among 4 persons, so each
person gets three things. Therefore. the total number of ways
12!
3! 3! 3! 3!
12xUxlOx9x8x7x6x5x4x3x2xl
=
6x 6 x 6 x 6
= 47900 1600 = 369600
6x6x6x6
Problem 40. There are six points on the circumference of a circle. How
many straight lines can be drawn through these points?
Solution: Here no three tJoints lie on a line and through any two
points, a straight line can be drawn. Therefore. the total number of lines that
can be drawn from 6 points
=6 C2
=~= 6x5 = 15
2! 4! 2 xl
Problem 41. Out of 6 teachers and 4 students, a committee of 5 is to be
formed. How many such committees can be formed including (i) at least
one student (ii) 3 teachers and 2 students?
Solution: (i) In this case we have to select at least one student; this
means that from one to all students are to be selected. So. there can be the
following formations, of a committee of 5 persons :
(a) 1 student and 4 teachers (b) 2 students and 3 teachers
(c) 3 students and 2 teachers (d) 4 students and 1 teacher
Tota I ways
.
III
(4C
case a) = I X
6
C4= I!4!3! x 4!6!2!
= 4 x 15 = 60
Total ways in case (b) = 4C2 x 6C3
4! 6!
::: 2! 2! x 3! 3! = 6 x 20 = 120
Total ways in case (c) = 4C3 X 6 C2
4! 6!
= 3!1! x 2! 4! = 60
~M~AT~H~E~M=A~T~IC=A~L~C~O~N~C~E=P~T~S~A~N~D~C~O~M~P~U~T=E~R___________________ 29
ways, event E happens or say m ways are favourable to the event E. Therefore,
the probability of event E is also given by
P(E) = Favourable number of ways to event E
Total number of ways of the experiment
Problem 43 : Find the chance of throwing more than 4 in one throw of
cubic dice marked 1 to 6 its six faces,
Solution: Here are 6 equalJy likely cases of which only 2 are favourable
because we want 5 or 6 on the upper face of the cubical dice. Hence, the
required probability of throwing more than 4 in one throw with one dice
2 1
=6=3"
Problem 44. In a single throw with two dices, what is the probability of
throwing 9?
Solution. The number of the first dice may appear in 6 ways. Similarly,
on the second dice also the number may appear in 6 ways. Hence, the two
dices may appear in 6 x 6 ways namely,
(1, 1), (1,2), (1,3), (1,4), (1,5), (1,6),
(2, 1), (2,2), (2, 3), (2, 4), (2,5), (2,6),
(3, 1), (3,2), (3, 3), (3, 4), (3,5), (3,6),
(4, 1), (4,2), (4,3), (4,4), (4,5), (4,6),
(5, 1), (5, 2), (5, 3), (5, 4), (5,5), (5,6),
(6, 1), (6, 2), (6, 3), (6, 4), (6,5), (6,6).
Out of these 36 ways, those which give desired sum of 9 are (3, 6), (4,
5), (5, 4) and (6, 3), i.e., only 4 favourable ways.
:. The probability of throwing 9 = 4/36 = 119.
Problem 45. A bag contains 5 white, 8 black and 3 red balls. If three balls
are drawn at random from the bag, then find the probability of the event,
(i) that all the balls may be white,
(ii) that one ball may be black and the other two white.
Solution. Total number of balls = 5 + 8 + 3 = 16.
Total number of ways of drawing three balls from the 16 balls in the
bag
C3 = ~ = 16. 15 . 14 = 560
16
3!13! 3.2.1
(i) Total number of ways of drawing three white balls out of 5
= 5 C3 = 10.
. .. The probability of drawing 3 white balls together
10 1
= 560 = 56'
MATHEMATICAL CONCEPTS AND COMPUTER 31
(ij) Total number of ways of drawing two white balls out of 5 and one
black ball out of 8
= 5C x 8C =80 .
2 J
So, number of ways of drawing three balls of which one is black and
the other two white
80
==
560 7"
Problem 46. Three cards are drawn from a pack of 52 cards. Find the
probability that:
(i) aU the three will be kings,
(ii) the cards are a king, a queen and ajack.
Solution. (i) Total number of ways of drawing 3 cards from a pack of
52 cards
C =~52X51X50=22100.
=52
3 3! 49! 3x2x 1
Number of kings in the packet is 4, so the favourable number of ways
of drawing three kings
4 4!
= C3 = 3! I! = 4.
So, the required probability
4 1
= 22100 = 5525·
(ii) The favourable ways are 4CJ x 4C J X 4C1 = 4 x 4 x 4 =.64 .
... Required probability
64 16
:::: 22100 = 5525·
Problem 47. Two cards are drawn from a pack of 52 Find the probability
that one may be queen and the other a king.
Solution. Total number of ways of drawing 2 cards out of pack of 52.
=~= 52 x51 x50! = 1326
=52C
2! 50!
2 2 x 1 x 50!
Now, number of favourable ways of drawing 2 cards together, of which
one is a queen and the other a king
4
=4 C1 X C 1 =4 x4 = 16.
.. . d probab·l·
the reqUIre 16 = 663·
I Ity = 1326 8
Problem 48. Two cards are drawn from a full pack of 52 cards. What is
the chance that (i) both are aces of different colours (li) one is red and other
is black?
32 PHYSICAL CHEMISTRYI
Problem 52: Define the terms maxima and minima and also mention the
conditions lor finding them.
[I] Definition
Let y =f(x) be some given function and x = a is some given point.
Suppose on the left hand side of x = a, there exists some nearest point
x = a /z and on the right hand side of x = a there exists some point
x = a + h, where h is very small.
At x =a f(x) =f(a)
At x =a  h f(x) =f(a  h)
At x = a + h f(x) = f(a + h)
Maximum: At x = a, the function is maximum, if
1(0  h) </(0) > I(a + h)
Minimum: At x = a, the function is mimmum, if
I(a  h) > I(a) </(a + h)
or ~=O
dx
34 PHYSICAL CHEMISTRYI
If for small and great nearest values of x = o'!:!x has same sign (either
L
(X
both positive or both negative), then at x = a, y :::: f(x) has neither maximum
nor minimum.
Problem 53 : (a) Find the maximum and minimum values of
x 3  3x 2  9x.
(b) Show that the function y = X S  5x 4 + 5x3  10 has a maximum at
x = 1, while minimum at x = 3 (Meerut 2007)
2
Solution: (a) f(x) = x 3  3x  9x
or y = x3  3.l  9x
Differentiating with respect to x
!!.l. = 3x2  6x  9
dx
MATHEMATICAL CONCEPTS AND COMPUTER 35
Problem 54. Show that in all the rectangles of the. same area, the sum of
the sides of the square is the least.
Solution. Suppose x and y are the length and breadth of a rectangle,
then its,
(a) Area =xy =A (given) ... (i)
(b) Perimeter" P = 2 (x + y) = 2 ( x + ~ ) [Using equation 0)]
.. P is a function of x, ~o for maximum and minimum value of P, we must
have,
Now
Now
2
d P
At x"'{;\, >
2
0
dx
Therefore, the perimeter (P) of the rectangle is least when x ={;\
1
or x =A =xy.
2
x =xy =H (x  y) == 0
=} x == Y ( ... x 0) *
So, all the rectangles with given area are square if the perimeter of
rectangle is least.
Problem 55. What is the maximum area of a rectangle of perimeter 176
em?
Solution. Suppose x and yare the length and breadth of the rectangle,
respectively. Then,
2(x+y)== 176 or x+y=88
Area, A == xy = x(88  x)
dA == 88  2x and
dx
dA =O=}x=44
dx
x=: 44 is a point of maximum.
Maximum area == 44 (88  44) = 44 x 44 = 1936 cm2•
MATHEMATICAL CONCEPTS AND COMPUTER 37
:. x = 1 is a point of minimum.
:. Minimum value = 1 + 1 = 2.
Problem 57: What is a linear graph? How will you calculate the slope
of a linear curve?
Solution: If a graph is plotted on two axes, say X and Y and we get a
straight line, then it is known as a linear graph. The equation of a straIght
line is y = mx + c, where m = slope which the line makes on Xaxis and c is
:::.......... '," .... .
Intercept
vt
B~~ o
X
x
m = slope = tar, e = (~)
m = slope = e
c = Intercept =AB =
c Intercept = 0
the intercept (or portion) cut by the straight line on Yaxis. This can be
represented by the curves shown in figures (1) and (2).
y=( ~)x+6
or 3y=2x+ 18
or 2x + 3y= 18
COMPUTER
Problem 58: Explain the terms functioning, characteristics, limitations
and components of a computer. (Meerut 2005. 04)
[I] Introduction to Computer
The word computer comes from the word 'compute' which means to
calculate. So, normally a computer is considered to be a calculating device
that can perform arithmetic operations at enormous speed.
Computer is an invention that has taken more than a hundred years to
take the shape it is in today. The way the nature of computers have manifested
in our lives, is slightly less than the effect that the discovery of fire or the
Illvention of the wheel had on evolution of mankind. Launching of a space
craft, making an airline reservatIOn, scheduling year, your day or keeping a
child occupied with some games is like a game for this wonder machine. The
essence being, computer can no longer be termed as a mere inventionit is a
revolution.
Computer can be defined as an electronic machille which processes raw
data to give meaningful if!formation. In other words, the term computer is
used to describe a device f//ade up of combination of electronic and electro
mechanical components.
Data : Data are collection of facts, figures, statistics which can be
processed to produce meanlllgful informations.
Processing: Proce~sing IS the manipulation of the letters, numbers or
graphic symbols that constitute data. It includes calculation, comparison,
decision making, logic.
Information: Information is the term given to meaningful form of
data. In other words, it is processed data.
Memory
Control Arithmetic
Unit and logical
urut
Now let us study each of the components:
C.P.u.: The central processing unit is also referred as 'brain' of the
computer. It controls the flow of data through the system, directing the data
to enter the system, placing data in memory, reentering them when needed
and directing the output of information. It consists of :
(a) Arithmetic Logic Unit (A.L.U.): It performs all the arithmetic
calculations and takes logical decisions. It can perform addition, subtraction
etc.
40__________________________________~P~H~Y~S~I~C~A~L~C~H~E~M~IS~T~R~Y~I
(b) Control Unit: This unit controls and coordinates the activities of
all other parts of a computer system. It performs the following functions:
(i) It can get instructions out of the memory unit.
(il) It can determine the storage from which it is to get the net
ll1structions after the previous instruction has been executed.
(iIi) It can decode the instructions.
(c) Memory: All the data, intermediate and final results are stored in
memory. It is used to hold the instructIOns to be carried out and the data to
be processed. It is c1as~ifled mto two types:
(i) Primary memory Oi) Secondary memory.
(i) Primary memory: It is also called the main memory or the central
memory. It is again of two types RAM and ROM.
RAM is essentially a 'ReadlWrite MemO/y'. Information can be written
into and read from a RAM. It is volatile in nature, i.e., it retains the stored
information as long as the power supply is not switched off. ROM is a
permanent type memory. ROM retains the data in it even in the absence of
power and IS thus nonvolatile storage. ROM does not allow user to write data
onto it. It stands for 'Read Only Memory'.
(ii) Secondary memory: It is found outside the CPU box and hence
~ometimes called external memory or the external storage. Examples are
floppy disks, t~lpe~. compact disks (C.D's) etc.
(2) Input Devices: These devices are required to get raw data into
the computer. It is considered as 'interface' between the user and the system.
Various types of input devices are as follows:
(i) Keyboard: It is just like a typewriter. But there are additional keys
that control functions. These are alphanulIleric keys, special keys and/ullction
keys.
(ii) Mouse: It is one of the most popular type of specialized input
deVIce for computers. It is used as a pointing device.
(iii) OMR: The 'Optical Mark Reader' is a device which is capable
of recognising prespecified type of mark made by pencil or pen.
(iv) OCR: The 'Optical Character Reader' cannot only detect a mark
but also recognizes its shape and identify characters directly from source
documents.
(v) Light pen: Light pen uses a light sensitive photoelectric cell to
a single screen position to the computer.
(3) Output devices: Output devices are those which output the pro
cessed information. These devices are as follows:
(i) Visual display unit: It is used for interactive processing. It is
commonly known as monitor.
(ii) Printers: The most common form of computer output is printed
output is also called hard copy. Printers are classified as/to how they print and
how fast they operate. Character printer, page printer and line printer are
different types of printers.
(iii) Storage: It has storage areas, often referred to as memory. The
memory can receive, hold and deliver data when instructed to do so. This
MATHEMATICAL CONCEPTS AND COMPUTER 41
fonn of storage stores the data permanently in the given media, examples of
which are floppy diskettes, magnetic discs, C.D's etc.
Problem 2 : Explain the binary system used in computers. Define the terms,
bit, nibble and byte.
Solution : Binary System : A computer interprets infonnation com
posed of only zeros and ones. So, instructions and data processed by a
computer must be in the fonn of zeros and ones. In other words. the data are
stored and processed as strings of two symbols or two state devices. A switch
is for example, a two state device, it can be either ON or OFF. As decimal
system uses total ten digits to make any number, similarly the binary system
uses only two digits (0 and 1) to represent any large number. Each character
in computer is represented by a number of decimal system and further con
verted into 0 and 1 (binary number). Since only two digits 0 and 1 are used
in the system, it is called, binary number system. The each digit of this number
system is called binary digit or bit. This system of numbers can also be said
as base 2 number system. In this system also each digit has its place value as
in decimal number system. The digit written at extreme left is called 'Most
Significant Bit' (MSB) and the digit written at extreme right is called 'Least
Significant Bit' (LSB). Note the place ofLSB and MSB in the example given
below.
1 o o o o 1
1
Most Significant Bit Least Significant Bit
f
(1) Bit. As it has already been stated above that each digit of binary
number system is known as 'Billat:v Digit'. To make its name short, the B has
been taken from Binary and IT is derived from Digit, thus making its name
as BIT. A bit represents the smallest part of memory locations in computer,
which stores either 0 or 1. Refer figure (3) for bit.
Binary
I
I 1 () 0 I 0 Blllary digit or bit.
number I, which represents
Power the smallest part of
24

2' .,6 25 23 22 21
of base computer memory
Decimal
equivalent 128 64 32 16 8 4 :2 Binary digits are
sho\',.11 in the form
ON / of switches. If any
switch is ON. It .
1 1 1 1 1 1 0 255
1 1 1 1 1 1 1 256
Problem 3 : Discuss the conversion of numbers from one system to another
with examples.
Solution: Conversion of Numbers: We know that computer under
stands only binary numbers, so the methods of converting the numbers from
one system to another, has been explained below :
(1) Decimal to binary conversion. The base of binary number system
is 2 because it uses only two digits to represent the number. The base of
decimal number system is 10 because total 10 digits are used to represent the
MATHEMATICAL CONCEPTS AND COMPUTER 43
2 1 8 5 1
2 9 2 1
2 4 1 0 I Remainders
2 2 0 1
2 1 0 0
2 5 0
2 2 1 (MSB)
1 0
Problem 4. Convert decimal number 742 to binary.
Solution. After dividing the number by 2, the remainder is noted in each
step. The last remainder will make most significant digit and first remainder
as least significant digit.
The binary number will be as follows :
(0 1 0 0 1 0 1 Oh = (742ho
(2) Binary to decimal conversion. As the numerals are converted to
binary system for storing into computer memory, these numbers are converted
back into decimal form for output purpose in the same way. The conversion
of these numbers is done automatic by the electronic parts fitted in computer.
For converting, binary numbers into decimal, following steps are to be fol
lowed.
(a) Find the least significant digit and most. significant digit in the
number.
(b) Mark the place position of each digit starting from LSB to MSB.
The first position will be zero position.
(c) Find the place value of each digit with the help of the following
formula,
Digit X Base number place pOSItIOn of digit.
It is important to note that the base value in binary system is 2.
(d) Add all the place values to get the equivalent decimal number.
This can be understood by the following problem.
Problem 5. Convert the binary number (1 0 0 1 0 1 Oh to its decimal
equivalent. (Meerut 2006)
44 PHYSICAL CHEMISTRYI
(d) Add all the place values to get the decimal equivalent number.
This can be understood by the following problem.
Problem 7. Convert (6 5 3 4 2)8 octal number to its equivalent decimal
number.
Solution.
Octal digit Place position Place value
4
(MSB) 6 4 6x8 24576
5 x 83
i
5 2 2560
3 2 3 x 82 ::: 192
4 1 4 x 8' 32
(LSB) 2 o 2 x 8° 2
:. Decimal equivalent number is:
24576 + 2560 + 192 + 32 + 2::: 27362
So, (6 5 3 4 2)g::: (2 7 3 6 2)10
(5) Decimal to hexadecimal conversion. An in binary number system
only two digits (0 and 1) are used and in octal ~stem 8 digits (0 to 7) are
used to represent the numbers, similarly in hexadecimal number system total
16 digits are used to store and represent the numbers. The digits are 0 to 9
and A to F, where A is used for 10, B for 11, C for 12, D for 13, E for 14 and
F for 15. The reason for using these alphabets in place of numbers is that each
digit should be represented by single entity. If we write 10 (i.e .. one zero) to
represent eleventh digit making it a combination of two digits i.e., 1 and 0,
which have already been used for representing the digits 1 (one) and 0 (zero)
independently, it will create confusion to recognise among the numbers 0, 1
and 10. So, t;:> avoid this confusion, alphabets from A to F are used to represent
numbers from 10 to 15.
As shown above, total 16 digits are used in hexadecimal system. While
converting decimal number to hexadecimal number, we divide decimal num
ber by 16 unless we get remainder less than 16 because the base of hexadec
imal system is 16. This can be understood by the following problem.
Problem 8. Convert (186275 2ho decimal number to hexadecimal.
Solution.
16 8 6 2 7 5 2
16 1 6 4 2 2 0 (LSB)
16 7 2 7 0 2
16 4 5 4 6
16 2 8 6
l~'
1 (MSB)
46 PHYSICAL CHEMISTRYI
I
LSB
A
C
2
2
1
0
Ax 162
ex 16
2 x 16°
1
= 2560
192
2
The decimal equivalent number will be :
327680 + 28672 + 2560 + 192 + 2 = 359106
or (5 7 A C 2)16 = (3 5 9 1 o 6)10
(7) Hexadecimal to binary conversion. The conversion of hexadecimal
to binary number is very simple just by converting each digit of hexadecimal
to its binary equivalent. To make it simpler. let us know the binary equivalent
of each decimal number from 0 to 15 as shown in tableI.
Table1. Relationship between the four number systems
Decimal Binary Octal Hexadecimal
0 000 0 0 0
I 000 I I I
2 0 o I 0 2 2
3 001 I 3 3
4 010 0 4 4
5 0 I 0 I 5 5
6 o I I 0 6 6
7 0 I I I 7 7
8 I o 0 0 10 8
9 100 I II 9
10 I 010 12 A
II I o 1 1 13 B
12 1 1 0 0 14 C
13 1 1 0 1 15 D
14 1 I 1 0 16 E
15 1 I 1 I 17 F
Example:
1111
11011
+ III
LaOOlO
(b) Subtraction: This method is also known as complementary sub
traction. We will be doing the following three steps to perform subtraction:
(i) We have to find the complement of the number we are subtracting.
(ii) To the complement of number obtained in step 1, we add the number
we are subtracting from.
(iii) If there is a carry 1, add the carry to the result of the addition, else
recomplement the sum and attach a negative sign.
Example: Number Complement
10001101 01110010
Consider the following example of subtraction.
Example: 1010101  100100
Step 1. Find the complement of 1001100
11011
Step 2. Add the number you are subtracting from
Carry 1110111
1010101
+ 0110011
0001000
+1 (Since there is a carry of 1)
0001001 7 Result
(c) Multiplication: The table to be remembered is :
Oxl=O
lxO=O
1 x 1 == 1
Example: 10101 x 11001
10101
11001
10101
00000
00000
10101
10101
1000001101 7 Result
(d) Division: The table 'for binary division is
Oil =0
1/1 = 1
The steps for binary division are:
(i) Start from the left of the dividend.
MATHEMATICAL CONCEPTS AND COMPUTER 49
flow of execution of the algorithm, i.e., they indicate the order in which the
instructions must be executed. Figure below shows the symbols commonly
used in flow charting.
C) Oval, indicates Start or Stop: tenninator symbol)
~"
Rhombus, used to specIfy a condition. This usuall)' takes the lorm of a
quesllon with possible answers Yes or No (or True or False).
These arrows lead to the reqUIred action corresponding to the answer to
the question (the decision symbol. more commonly called the decIsIOn
o
box).
•
52 PHYSICAL CHEMISTRYI
a single user. Thus, operating systems (OS) for PCs have been constructed as
a single user single task operating system, i.e., it is assumed that only a single
user uses the machine and runs only one program at a time. The operating
system of PCs consists of two parts, viz.: (i) Basic Input Output System (BIOS)
which is stored in a floppy disc or a hard disc and (ii) Microsoft Disc Operating
System (MS DOS). This type of OS is widely used. The BIOS provides basic
low level services, whereas DOS provides many userlevel services. MSDOS
provides services such as editing, filing and other utility programs.
MSWindows is an improved operating system for more powerful per
sonal computers which have a large memory (4 to 8 MB) and disc (200 to
400 MB). This gives a very good 'Graphical User Interface' (GUI) which
simplifies the use of the computer. It also helps us; to allow the multiple
programs to be simultaneously stored in memory and executed.
(1) UNIX operating system. This system is a very powerful operating
system used in personal computers and supercomputers. UNIX is written in
C, so it makes it portable. It is organised as a layered operating system. The
innermost portion is known as a kernel. It provides lowlevel services, e.g.,
device drivers and memory management. The next portion is known as a shell.
It is a command interpreter. The outermost portion is known as utilities
portion. It provides miscellaneous services such as text processing, text set
ting, games, calender, graphics, language compilers etc. The user interacts
with the kernel using commands and utilities.
EXERCISES
[I] Numerical Problems
1. FIII Illerentl'al coe ff"IClent 0 f,log x .
' d the d'''''
x
2. Calculate the value Of: if Y! = tf'y.
3. Evaluate f5 dx,
(d) 25
2. Values of 8C3 and 9P2 are respectively:
(a) 28, 72 (b) 56, 72 (c) 56, 36
(d) 28,36
f~
3
3. The value of is :
1
(a) log 3 (b) log 2
(d) log 10 x
(a) ~
5
(b) ! (c) 
6 7
7
(d) 12
6. Value of !x 72
/ is :
(d) * 5
log (x + 4)
54 PHYSICAL CHEMISTRYI
11. The unit used to read the exernal data and instructions in a computer is :
(a) Input unit (b) Output unit (c) CPU
(d) None of the above
12. The computer memory is measured in terms of :
(a) Units (b) Bytes (c) Binary
(d) ALU
13. The decimal equivalent of (IOOlllh is :
(a) (19)10 (b) (29)10 (c) (39)10
(d) (49)10
14. I second consists of ...... microseconds :
(a) 10
3
(b) 106
(d) 1012
15. The following is an output device:
(a) Keyboard (b) Arithmetic logic unit (c) Monitor
(d) Scanner
3. f2 x 3dx =
I
3l
4. The value of probability varies from  I to I.
5. For a straight line 2y = 3x  3. the intercept on Yaxis is  3.
6. The speed of computer is very fast as compared to a calculator.
7. A computer consists of CPU only.
8. The computer memory is measured in terms of bytes.
9. In computer memory, 0 and I are called binary digits or bits.
MATHEMATICAL CONCEPTS AND COMPUTER 55
ANSWERS
[I] Numerical Problems
1.
llogx
2.
logx k 2
3. 2x2 4. 3a (ax + b)3/2
x2 (I + logx)2
S. 4 6. (27.101)10 7. (IOOIOOIOh 8. (IOOlllh
9. (0.0727024)8 10. (100101111 lh
000
GASEOUS STATE
Problem 1 : What is the nature or significance of R in general gas equation
PV = nRT? Calculate its value in different units.
Nature or significance of gas constant R. From general gas equation,
PV=nRT
R = PV = Pressure x Volume ... (1)
IlT Mole x Temperature
Force Force
Pressure =  =
Area (Length)2
R = PV =Lx 22.4
.. T 273
= 0.0821 litre atmosphere deg1 mole1
(2) Value of R in erg deg 1 mole 1
P = 76 x 13.6 x 981dyne/sq cm, V= 22400 ml, T= 273 K
PV 76 x 13.6 x 981 x 22400
R=T= 273
= 8.314 x 107 erg deg 1 mole1
(56)
GASEOUS STATE 57
1 2
or PV=3"mIlU ... (4)
or PV = ~ k = constant
T 3
60 PHYSICAL CHEMISTRYI
Voc p1 , at constant T
or PV = constant, at constant T.
From kinetic equation, we have,
1 2 2 1 2
PV=mnu = Xmnu
3 3 2
The kinetic energy of the gas, E = ~ mnu
2
2
PV=·E ... (2)
3
At constant temperature, kinetic energy (E) of the gas is constant.
PV = constant.
This is Boyle's law.
(ii) Charles' law : According to it, 'at constant pressure, the volume
of a given mass of a gas is directly proportional to its absolute temperature, '
i.e.,
Voc T, at constant P
As already derived, from equation (2), we have
2 2 E
PV =3 . E or V =3 . P
At constant pressure,
V = constant X E or VocE
But we know that E oc T, where T is absolute temperature.
.. Voc T
This is Charles' law.
(iii) Avogadro's hypothesis: According to it, 'equal volumes of all
gases under same conditions of temperature and pressure contain equal
number of molecules '.
For any two gases, the kinetic equation can be written as,
1 2 2 1 2
PI VI ="3 mllllul ="3 X 2" mlll\U\
1 2 2 1 z
Pz V2 = "3 11121l 2U 2 ="3 X 2" m21l 2UZ
=G~AS~E~O~U~S~ST.~A~~=E ___________________________________ 61
When pressures and volumes of the gases are the same, i.e., PI = P2
and VI = V2 , it follows that,
When the gases are also at the same temperature, their mean kinetic
energy will also be the same, i.e.,
121 2
2" mIuI = 2" m2u2 ... (4)
pv=imnu2 or u=~=~
mn _ Total mass of the gas  d
(As V  Vi I
.
 enslty 0
f th
e gas,
d)
oume
Therefore, at constant pressure,
The rate of diffusion (r) of the gas is directly proportional to the mean
velocity (u) of the molecules, i.e., u oc r.
I
rocTd'
This is Graham's law of diffusion.
(v) Dalton's law of partial pressures: Suppose ni molecules each
of mass m) of a gas A are contained in a vessel of ,:,olume V. Then, according
to the kinetic theory, the pressure, PA of the gas A will be given by,
1 mInIuI
PA=3"V
Now, suppose n2 molecules, each of mass m2 of another gas Bare
contained in the same vessel at the same temperature and there is no other
gas present at that time. The pressure, PB of the gas B is then given by,
2
1 m2n 2u2
PB=3"V
62 PHYSICAL CHEMISTRYI
If both gases are present in the same vessel at the same time, the total
pressure, P is given by,
1 mllllUr 1 m2n2u~
P=3V+3V=PA+PB
Similarly, if three, four or more gases, e.g., A, B, C, D, etc are present
in the same vessel, the total pressure is given by,
P=PA +PB+PC+PD+ ...
This is Dalton's law of partial pressures.
(b) Kinetic Energy of One Mole of a Gas
According to kinetic equation of gases, for one mole of a gas,
1 2
PV = 3 mNu (where N = Avogadro's number)
2 1 2
or PV=xmNu ... (5)
3 2
The kinetic energy (E) of one mole of a gas is given by,
1 2
E=mNu
2
Thus, from equation (5),
2
PV=3. E=RT
3
m E=jRT
* We will use the term molar heat instead of specific heat, as in chemistry it is customary to
use the term molar heat. Morwver,
molar heat = specific heat x molecular weight.
GASEOUS STATE 63
E=lRT
2
Similarly, kinetic energy (E1) per mole at temperature (T + 1).
3
E1=R(T+I)
2
Increase in kinetic energy per mole for one degree rise in temperature
is given by,
3 3 3
E1E=2 R (T+ 1)2 RT =2 R
where, dnc is the number of molecules with velocities in the range c and
c + dc, n is the total number of molecules of the gas, M is the molecular weight
of the gas, T is the absolute temperature, c is the lower value of velocity for the
selected velocity range, dc is the velocity interval for the velocity range, e is a
mathematical constant, base of natural logarithm, whose value is 2.71.
DiVIding equation (1) by dc, we get
~ . dll c _
n
(JL) 
dc  4n 21tRT
3/2
.e
M/I2RT
.c
2
... (2)
:: '"
<I)
"3
u
<I)
'0
'.'
:::8
.....0 :;':
r. ;';.
<I)
.. ~
" .
E<I)
.'. ~
<I)
p...
: ''
:
.'.
....
.'.
·1
~ :::.
ii . . . . . . . . . . . . . . . ~. 2. '"""b;~.:M:::~ V"'~ty.;if.;;..;t!
This is the usual form of the equation for Maxwell's law of distribution
of velocities.
The left hand side of expression (2) gives the probability, p of finding
molecules having the velocity c. This is virtually (not exactly) the fraction of
the molecules having the velocity c. Knowing the molecular weight of the
gas, we can calculate the fraction of the molecules having any particular
velocity c, at any desired temperature.
The general form of distribution of molecular velocities is shown in
figure 2. Fractions (percentages) of the molecules having various velocities
are plotted along Yaxis and velocities are plotted along Xaxis. The actual
curve depends upon the molecular weight of the gas and temperature, but the
general form of the curve is the same for every gas.
From the curves, it is seen that the fraction of molecules having veloc
ities greater than zero goes on increasing with increase in velocity, reaches a
maximum value and then begins to fall towards zero again for very high
velocities.
GASEOUS STATE 67
Problem 6 : Define the terms average velocity, root mean square velocity
and most probable velocity of molecules and how are they related to each
other? (Meerut 2006)
Or, Find out a relation between RMS velocity and average velocity.
(Meerut 2005)
Or, Define root mean square velocity a1ld average velocity. (Meerut 2007)
2+ 2+ 2+ ... + 2)
~(
. _ UI U2 U3 Un
RM.S. velocIty 
11
(iii) Most probable velocity (a. or u): It is defined as, 'the velocity
possessed by the l1laximum number of molecules of the gas '.
The relationship of most probable velocity to the average velocity and
root mean square velocity can be developed from the following expressions:
or u="C::)=~(3~T)
where, \ mN = M =molecular weight
8.31~X 10 T)
7
.. u = "(3 X X
or II
4
= 1.58 X 10 X " ( ~)
Knowing the value of T, we can calculate u.
GASEOUS STATE 69
PV=~mN1l2=~MU2 or u~vC~V)=V(~)
[As d = MIV = density]
Knowing the values of P and d, we can calculak u.
Problem 8 : What are real and ideal gases? In what respect does a real
gas differ from an ideal gas? (Meerut 2004)
(ii) The volume of a real gas does not become zero at 273°C. In fact,
when cooled sufficiently, a real gas is suddenly converted into liquid state.
Problem 9 : (a) What are the limitations of the equation PV = RT? Show
in what respects vander Waals equation is an improvement over the simple
gas equation. Derive vander Waals equation and discuss it or write the
drawbacks of this equation.
(Meerut 2004, 03, 01, Garhwal 2006, 02, 2000,
Kanpltr 2005; Agra 2006, 01.2000)
Or, Discuss vander Waals equation of state in detail. (Meerut 2005)
Or, Explain vander Waals equation along with volume correction and
pressure correction. (Meerut 2007)
(b) What are the units of vander Waals cOllstants. (Meerut 2003, 2000)
(c) Show that effective volume of the gas molecules is four times
greater thall the actual volume of the molecules. (Meerut 2002)
..
i
...'"
(1)
(1)
>, A
c:>.
'"
J
~
(1)
~
>Po.
..
15
200 400 600 800
PAtmosphere _
GASEOUS STATE 71
i
p+ ... (2)
2 2 \
':poc nd oc n naJ
v2 =7
2 2
between the molecules become too small. So, the correction term alVz, due
to attraction factor is negligible even at ordinary temperature or low pressure.
Therefore, equation (1) becomes,
P (V  b) =RT or PV =RT + P.b =(PV)ideal + P.b
This explains the rise in the curves of Hz and He with an increase of pressure
right from the very beginning even at ordinary temperatures or low pressures.
(b) Units of vander Waals' Constants
From equation (3), the constant a is expressed by PVzII?, i.e., pressure
x (volume)2/moI2. If pressure is expressed in atmospheres and volume in
cm 3 the value of a will be atm cm6 moCz. If volume is expressed in litre (or
dm 3 ), the value of a will be atm L2 mol2 or atm dm 6 mol 2. In Sl system.
the unit of a will be
(Nm2) (m 3)2 42
ry or Nm mol.
(molt
The constant b is incompressible volume per mole of a gas so, it will
have the same units as volume per mole, e.g., cm3 moC I , L mor) or
dm 3 molI. In SI units, the unit of b will be m 3 molto
(C) Effective Volume of Gas Molecules
vander Waals suggested that a
correction term nb should be sub
tracted from the total volume V in Excluded
order to get the ideal volume which is Volume
compressible. In order to understand
the meaning of the term lib we con ,,
I
tance r. For this pair of molecules. ;: :;:;: :/: : ,: : : : : : :;. . ~.i~: .~. . .r::::::':::}:.:':':':' ..:
therefore, a sphere of radius r and of
vo Iume 3"4 1[r3 constItutes
. wh
at 'IS
known as excluded volume or covolume. The excluded volume per molecule
is thus half the above volume, viz., ~ 1[,.3. The actual volume of one gas
· r I 'IS "3
mo IeeuIe 0 f ra dIllS 4 /1
1[r·. S 0,
4
31[r'
':1 4 (r}3 =61[1"
=31[l2
1 3
GASEOUS STATE 75
2
:. Excluded volume per molecule == 31tr
3
1 3
== 4 X 1tr
6
== 4 x Actual volume of the gas molecules.
Problem 10: What do you understand by critical temperature and critical
pressure in relation to vander Waals' equation and critical phenomenon.
Calculate the values of critical constants in terms of vander Waals' con
stants. How are the values of critical constants determined experimentally?
(Meerut 2002; Agra 2005,03,01; Rohilkhand 2005,01; Kanpur 2006)
Or, Starting from vander Waals' equation find the values of critical con
stants.
Or, Write a short note on continuity of state. (Meerut 2002, 2000)
Or, Define critical temperature. (Meerut 2(06)
The curves which are obtained by plotting pressure against volume at
various constant temperatures are known as isotherms (isos == equal;
therm:::: heat). Andrews obtained isotherms of carbon dioxide at different
temperatures which are shown in figure (7).
First consider the isotherm ABCD at 12.1 Dc. The point A represents
CO 2 in the gaseous state occupying a certain volume under certain pressure.
On increasing the pressure, the volume of the gas decreases along AB in
accordance with Boyle's law until at a certain pressure (at B) liquefaction
occurs. Further, decrease of volume is not accompanied by any change of
pressure, as shown by horizontal portion BC, until the vapour has been
condensed completely at C. The liquid is only slightly comp;'essible, so further
increase of pressure produces only a very small decrease in volume. This is
shown by a steep line CD which is almost vertical. Thus, along the curve AB,
CO 2 exist as a gas. Along BC, it exists partly as gas and partly as liquid.
Along CD, it exists completely as liquid.
At higher temperature (21. 1°C). a similar isotherm EFGH is obtained.
It differs from the first isotherm ABCD in two respects. viz .• (i) liquefaction
starts at a higher pressure and (ii) length of the horizontal portion of the curve
becomes shorter. With further rise in temperature, the horizonal portion grad
ually decreases until it is reduced to a point J and the isotherm becomes
continuous as seen in the isotherm UK at 31.1°C. So. there is no horizontal
portion of the curve and no sudden change from the gaseous to the liquid
state. At this temperature (31.1 ° C), the gas passes into the liquid state without
any visible separation of one phase from the other. This is called continuous
transition of state. The idea of continuity from the gaseous to liquid state can
be explained from the isotherm UK. The change at J shows no sharp discon
tinuity but a continuous transition occurs during the conversion. Above
31.1°C, the isotherms are continuous and there is no evidence of liquefaction
at all.
76 PHYSICAL CHEMISTRYI
(p+ ~2)cVb)=RT
may be simplified as,
a ab
PVPb+V v2 RT=O
V3 _ b V 2 + a V _ ab _ RW == 0
p p p
Arranging in descending powers of V, we get
V3 (b+ RT) 2
p V +aV p == 0
p _ ab ... (1)
This equation is cubic in V and as such there may be three real roots
or one real and two imaginary roots of V for each value of P and T. In other
words, for given values of P and T, there will be either three real values or
one real and two imaginary values of V. This behaviour is not shown by
isotherms of CO2 in figure (7).
At 51° and 31.1°, there is only one volume for each pressure. At
12.1°, there are two different values of V corresponding to points Band C for
the same pr~ssure. However, the third volume predicted by equation (1) is
missing.
By substituting the experimental values of a and b in equation (1),
Thomson (1871) calculated the values of V for different values of P and T.
He plotted these calculated values of V against P and the isotherms obtained
by him are shown by dotted curves in figure (7). The isotherms for temperature
31.1° and above are exactly of the same form as obtained by Andrews.
However, the theoretical isotherms below the critical temperature differ from
experimental isotherms (of Andrews). They have no sharp breaks and the
horizontal portIons of the curves are replaced by wave like portions. For
example, the experimental isotherms ABCD and EFGH are replaced by
theoretical isotherms ABB 1B 2B 3CD and EFF j F2F 3GH, respectively. In these,
there are obviously three volumes represented by B, B2 and C (and F, F2 and
G), corresponding to one pressure as predicted by equation (1). As the tem
perature rises, the wave portion of the curve becomes smaller and smaller and
the three values of volume get closer and closer until they merge into one
point J at 31.1 ° (critical temperature). At J, the three roots of V (say x, y and
z) of equation (1) are identical. Since the temperature is critical, the value of
V represents the critical volume of the gas, i.e., V == V,.. The three values of
V can be represented as,
(V x) (V y) (V  z) == 0,
At critical point, x==y==z== Vc
(V vi ==0
Expanding and writing in decreasing powers of V, we get
• .3
V  3 vy2 + 3 V~2 V  Vc3 == 0 ... (2)
This equation must be identical with vander Waals' equation (1) at
critical temperature and pressure, which may be written as
78 PHYSICAL CHEMISTRYI
,.3 ( RTc) 2 aV ab
V  b + Pc V + Pc  Pc = 0 " .(3)
Since equations (2) and (3) are identical, the coefficients of equal
powers of V in the two equations must be equal to one another. Therefore,
RTc
3V(=b+ p ... (4)
r
V3 = ab ... (6)
c Pc
Dividing equation (6) by (5), we get
Vc= 3b ... (7)
Substituting the values of Vc in equation (5), we get
P =~= a a ... (8)
c 3~ 3 X (3b)2 = 27b 2
Substituting the values of Pc and Vc in equation (4), we get
=~. PrY,. =~. (a/27b ) x 3b
2
T
(' 3 R 3 R
Sa
or T{,'= 27bR ... (9)
Determination of Critical
Constants
(a) Critical temperature and critical
pressure : These values can be determined
by a simple method which is based on the
principle that at the critical temperature, the
surface of separation, i.e., meniscus between
the liquid and the vapour phase disappears.
It is generally used when the substance is in
liquid state at ordinary temperatures.
The experimental liquid is taken in a
vessel V enclosed in a glass jacket J. The
temperature of J can be varied gradually by
circulating a suitable liquid from a thermo
stat. The vessel V is connected to a mercury
manometer M containing air. The tempera
ture is first lowered so that the vessel is
cooled and the surface of separation between
the liquid and its vapour becomes sharp. The ig.8. Apparatus for determining
temperature of the jacket is raised slowly. t;:l_ _ _ T.;.:<o..;a;;;;n.;;;.d.;;.Prr._ _u
This rise is continued till the meniscus be
GASEOUS STATE 79
tween the liquid and its vapour just disappears. This temperature say t~ is
noted. The jacket is then cooled slowly till cloudiness due to the condensation
of vapours appears again. This temperature t~ is again noted. The critical
(a) (i) vander Waals' equation explains the deviations of gases from
Boyle's law. Regnault and Amagat showed that gases at low temperatures and
high pressures do not obey the simple gas laws.
(ii) vander Waals' equation explains the critical phenomenon, whereas
simple gas laws do not.
(b) In problem 10, we had derived the following three equations:
RT,.
3V,.=+b ... (1)
Pc
V~ = ab ... (3)
Pc
Dividing equation (3) by (2), we get
V,
Vc::: 3b or b=3 ... (4)
RTc
or 8b= or ... (8)
Pc
From equations (4) and (8),
3RTc
or PC=8l1
c
Substituting the value of Pc in equation (7), we get
27 x 8R2~Vc
a = :====
64 X 3RTc
9
or a =gRT,yc
1 RT,.
and b = .  [From eq. (8)J
8 Pc
Problem 12 : Write short notes on the following:
(1) Various equations of state.
Or, Kammerling Onnes' equation. (Meerut 1989)
(2) lAw of corresponding states and its applications.
(Meerut 2004, 01; Kanpur 2005,02, Rohilkhand 2004,02, Garhwal2006, 03, 2000)
(3) Mean free path.
(4) Critical phenomenon and its utility.
(5) Collision frequency.
(6) lAw of equipartition of energy.
(7) Specific heat ratio. (Meerut 2004, 02)
(8) Boyle temperature. (Meerut 2(01)
(9) Continuity of state. (Meerut 2002, 2000)
p+ a 2](Vb)=RT
[ T(V + c)
82 PHYSICAL CHEMISTRYI
where. c is a new constant. This equation is fairly satisfactory but does not
hold good for all gases.
rIl] Dieterici equation: Dieterici introduced an exponential factor
to account for the effect of molecular attraction on the pressure. His equation
is given by.
P (V  b) = RT. eaiRTV
where. e is the base of natural logarithm. This equation gives more satisfactory
results at high pressures than the vander Waals equation.
[III] Berthelot's equation: Berthelot proposed the following empir
ical equation to explain the behaviour of real gases.
(p+ ;2)(Vb)=RT
The factors A. B, C and D etc. are known as first, second, third, fourth
etc. virial coeffreients (Greek: virial = force).
At low pressures, the coefficient A (which is equal to RD is important
and others cancel out. At increasing pressures, other coefficients become
significant.
[V] BeattieBridgemann equation: This empirical equation is given
by:
PV=RT+~+~+ ~ +...
where, p, y, 0 are also called virial coefficients.
2. Law of Corresponding States
vander Waals showed that if P, V and T of a gas are expressed in terms
of critical pressure, critical volume and critical temperature of a gas, we obtain
another important generalisation, known as law of corresponding states.
P V •
Let, =n
P('
=cj>
, V('
and L=9
1'..
where n, cj> and 9 are known as reduced pressure, reduced volume and reduced
temperature, respectively. Therefore,
P=nPc ; V=cj>V(' and T=9T,,,
Substituting the values of P, V and T in vander Waals equation, we get,
GASEOUS STATE 83
(p+ 0 }(Vb)=RT
[
n .~
27b
+ a2 2]
<I> (3b)
8a
(<I> • 3b  b) = R a . 27 b R
1= v ... ( 1)
..J(2). nva2nl ..J(2).na2nl
For n g mole of an ideal gas
PV=nRT=!!J..RT
N
where, N = Avogadro number.
N
z 1 2 2
==~·nvaN
2 '12
c
So, collision frequency of a gas increases with increase in temperature,
molecular size and the number of molecules per millilitre.
GASEOUS STATE 85
1212121 2
"2 mu
=2"mux +2"muY +2"muz
According to law of equipartition of energy,
1.2 mux2 = 1.2 mti.y = 1.2 mu z2 = 1.2n
RT
mole. The total energy is ~ RT. so the molecular heat capacity will be ~ R.
For diatomic gases: A gas where molecule has more than one atom
will have rotational energy and vibrational energy besides the translational or
kinetic energy. For diatomic molecule, this velocity will be only in one
direction, i.e., parallel to the axis of the particle. So, such a molecule possesses
two degrees of freedom, one for potential energy and the other for kinetic
energy.
Now consider the rotational motion. Due to collision with other mole
cules, the molecule will rotate about its own centre of gravity. Assuming the
velocity to be in one plane, it can be resolved along two axes and each axis
will have one degree of freedom.
Therefore, for a diatomic gas molecule, the translational energy will
have four degrees of freedom, two due to rotation and two due to vibration.
If the molecule is rigid, there will be no degree of freedom due to vibration.
So, the energy will be %RT.
Molecular heat capacity = %RT "" 5.0 calories
9. Continuity of State
See problem 10.
Problem 13 : Mention the various methods that are adopted for producing
cold and what is the lowest temperature hitherto attained? How has it been
reached? Show how these have been used in the liquefaction of gases ?
Mention the importance of liquefaction. What is inversion temperature.
(Meerut 2002,2000; GarhwaI2001; Rohilkhand 2002)
I
y
(p + n~ ) (V  nb) = nRT.
The units of a and bare lit2 atm mole2 and lit mole1, respectively.
6. Inversion temperature, Tj = ~
NUMERICAL PROBLEMS
Ex. 1 : (a) Calculate the kinetic energy of two moles of CO 2 at 300 K,
assuming it to be an ideal gas.
(b) Calculate in ergs the kinetic energy of a monoatomic gas (molecular
weight 20.2) molecule, moving with a velocity of 5 x 1(/ cm/s.
Solution: (a) The kinetic energy (E) of 2 moles of an ideal gas is given
by:
E=lnRT
2
3
E="2 x 2 x 8.314 x 300 = 7482.6 J.
U \113"21
= 1.58 x 104 x  F273)
u=v'e:)
p = 760 mm = 76 cm = 76 x 13.6 x 981 dynes/sq cm and D = 0.00009
g/cm 3•
7
_  '(3 x 8.314 x 10 x 298) 4 8 104 I
U  " 32  . x em s
T = 25 + 273 = 298 K; M = 32
= 1.58 X 104 x ~(~) = 1.58 X 10 ~(3~)
4
(b) u x
(b) Find out the RMS velocity for CO 2 gas at 12·C and 78 cm pressure.
Solution: (a) The RMS velocity is given by
... ( 1)
2
p= 74 x 13.6 x 981 dyne em ; M=32
92 PHYSICAL CHEMISTRYI
V == 76 x 74
22400 x 300 == 252806
x 273 • . C.c.
== 1.58 x 10
4
~(33020J
The RMS velocity (lI2) of S02 mblecules at T K
== 1.58 X 10
4
~F)
U
=
"
'(3P)
d
=_
"
'(3 x 76 x 13.6 x 981) =46137 6
0.001429 • em s
1
S I ti •
o u on. u"
=  '(3P) =
d "
'(3 X 76 X 13.6 X 981) = 145899
1.429 • ems
1
· u = ~(3P)
· : RMS veIoClty
So Iu t Ion  = ~(3 x 76 x 13.65x 981)
d 9 X 10
4
= 18.38 X 10 em S1
Average velocity =0.9213 xu = 0.9213 x 18.38 x 104 em SI
= 16.93 X 104 em SI
Ex. 11 : Calculate the pressure exerted by 1023 gas molecules each of mass
1022 g in a container of volume 1 Utre. The RMS velocity is Iff cm/sec.
22
Solution : Weight of 1023 gas molecules = 1023 x 10 g = 109
23
. 23 10 x 6.023 X 10
:. Weight of 6.023x 10 gas molecules = 23 = 60.23
10
:. Molecular weight, M = 60.23,
Let pressure = P cm
u=~3~V
5 /
10 cm see
= '[3 x (P x 13.6 x 981 dynes/cm2) x 1000
" 60.23
ml]
_ (105)2 X 60.23 _
or P  3 x 13.6 x 981 x 1000 15,040 em.
94 PHYSICAL CHEMISTRYI
Ex. 12 : The specific heat at constant volume of argon is 0.075 and its
molecular weight is 40. How many atoms are there in its molecule?
Solution: Molar heat at constant volume (CI')
= Specific heat x Molecular weight
= 0.075 x 40 = 3
Cp =Cv +R=3+2=5
Cp 5
Y= C
v
=3" = 1.66
Argon is thus monoatomic. i.e., there is one atom in its molecule.
Ex. 13 : The specific heats ofa gas at constant pressure and constant volume
are 0.125 and 0.075 cais, respectively. Calculate the molecular weight of
the gas.
The specific heat and molar heat are related as :
Molar heat = Specific heat x Molecular weight
.. Cp=cpxM andCv=cvxM andCpCv=R
Therefore, Cp =0.125 M and C v = 0.075 M
.. 0.125M  0.050M = R
2
or 0.050M = 2 or m = 0.05 = 40
Ex. 14 : The specific heat of a gas at constant volume is 0.152 and that at
constant pressure is 0.215. Calculate the atomicity and molecular weight
of the gas. Also name the gas.
Solution: Molar heat = Specific heat x Molecular weight
.. Cp=cpxM and Cv=cvxM
.. Cp =0.215M and C v =0.152M
Cp C v =2
0.215M  0.152M =2 or 0.063M =2
2
or M = 0.063 = 31.74
Y= Cp = 0.215 = 1.41
Cv 0.152
.'. Molecular weight of gas = 31.74
Atomicity = 2
Name of the gas = Oxygen.
Ex.1S : The specific heats ofa gas at constant volume and constant pressure
are 0.090 and 0.45 calories. If the atomic weight of the gas be M, calculate
its molecular weight.
GASEOUS STATE 95
We know that,
Molar heat = Specific heat x Molecular weight
Cp 0.125
Y= C = 0.090 = 1.38:::: 1.40
v
So, the gas is diatomic and so its molecular weight = 2 x M
.. Cp =0.125 x 2M =0.250M
and Cv =0.090 x 2M =0.180M
CpCv=R
0.250M  0.180M = 2 or 0.070M = 2
2
or M =0.070 = 28.57
:. Molecular weight of the gas = 28.57
Ex. 16 : Calculate the constants a and b, if Tc =31"C, Pc = 72.8 atm and
R = 0.082 lit atmldeg.
The values of Tc and Pc are given by:
P =_a_ ... (1)
c 27b 2
8a
Tc= 27bR ... (2)
Dividing (2) by (1), we get
Tc 8b 304 8b
 =  or     
Pc R 72.8 0.082
.. b = 0.0428 lit mole1
Substituting the value of b in equation (1), we get,
72.8 = a
27 X (0.0428)2
or a = 3.6 Iit2 atm mole2
Ex. 17 : The critical temperature and critical pressure of ethane are 305.1
K and 48.1 atm respectively. Calculate its vander Waals constants 'a' and
'b'.
Solution: As in Ex. 16, we can write,
Tc 8b 305.1 8b
 =  or   =  
Pc R 48.1 0.082
27 x (0.031S)
=1.357 8tm Iit2 mole2
Ex. 19 : The vander Waal\' constants in lit atm/mole of CO 2 are : a = 3.6,
b = 4.28 X 102• Calculate Tc and V(Jor the gas.
The values of Vc and Tc are given by,
Vc= 3b ... (1)
Sa
Tc = 27bR ... (2)
2
From (1), Vc = 3 x 4.2S X 10 = 3 x 0.042S = 0.1284 lit
P +!!l.. (VI  b l ) = RT
~
(V2  b 2) =RT
When al = a2 , then VI  b l = \/2  b2
The gas which has higher value of b will occupy more volume.
GASEOUS STATE 97
Ex. 21 : One mole oj NH3 is enclosed in afive litre flask at 27°C. Calculate
the pressure oj NH3 using vander Waals equation. For NH3, a = 4.17 atm
lif mole2 and b = 0.0371 lit moleto
Solution: vander Waals' equation is given by,
(p+ ~ )cVb)=RT
Substituting the values, we get
pc + ~ )(V b) = RT('
or V3  (RTc a V=O
b+ V2 + ab
Pc Pc Pc
\
At critical point, the three values of volume are identical and equal to
Vi.' Thus, .
(V vi=o
or V3  3 Vc y2 + 3 ~V  V~ = 0 ... (2)
As (1) and (2) are identical. therefore.
3Vc =b+
Rt ... (3)
pc
... (4)
... (5)
or b= Vc ... (6)
3
Substituting the value of b in equation (3), we get
Vc RTc Vc RTc
3V =  +  or 3V   = 
c 3 Pc c 3 Pc
98 PHYSICAL CHEMISTRYI
PV=nRT or P= ~T
P = 2 x 0.082
5 x 300 =9.84 a tmosph eres.
or P = 235.8 =9.43
25
Pressure = 9.43 atmospheres.
GASEOUS STATE 99
Ex.2S : Calculate the pressure using (i) vander Waals' equation and (ii)
ideal gas equation of 10 g ammonia contained in a 1 litre flask at O·C.
(a = 4.17 atm litr; mole", b = 0.0371 litre moleI)
Solution: (i) Using vander waals' equation
or P = 13.1843
1442
.0.9782
= 12.036 atm
(ii) Using ideal gas equation
PV=nRT
PV==nRT
p==nRT == 1 x 0.082 x 300
V 1.5
or P == 16.4 atmospheres
(ii) From vander Waals equation:
(p+ ~2)(Vb):::::RT
or p + ~21 (l.5  0.04) == 0.082 x 300
( (1.5) )
or lp /5) x
I 1.46::::: 0.082 x 300
or P == 0.082 x 300 _ _
1 == 16.183
1.46 1.5
Pressure == 16.183 atmospheres.
Ex. 28 : For NO gas, vander Waals' constant, b == 0.02788 lit/mole, calcu
loJe the diameter of NO molecule. (N::::: 6.023 X Itf.1)
10 x ~ x 3.14 x r3
23
or 27.88 == 4 x 6.023 X (b == 27.88 cc/mole).
3
or r3 == 2.76 X 10 cm 24
or r == 1.4 X 108 cm.
:. Diameter of NO molecule == 2 x 1.4 X 108 == 2.8 X 108 em.
Ex. 29 : For hydrogen the vander Waals' constants a and bare 0.246 and
2.67 x 101 in lit atmosphere units. Calculate the inversion temperature for
hydrogen.
2a
Solution : We know that. Ti== b.R
2 x 0.246
or T, == 0.0821 x 0.0267 ::::: 223.6 K
Inversion temperature. T; == 223.6 K or  49.4°C
. B' C'
(iii) PV=RT+Rr+R'f3 + ... (Iv)PV=RT+y+y+ ...
9. At 2TC the kinetic energy of 2 moles of an ideal gas is :
(i) 1800 cal (ii) 900 cal (iii) 600 cal (iv) 3600 cal
10. The following is called a permanent gas :
(i) NH3 (ii) N2 (iii) H2 (iv) CO2
11. The ratio of most probable, average and root mean square velocity is :
(i) I: 1.224 : 1.128 (ii) 1 : 1.128 : 1.224
(iii) 1 : 1.128: 1.524 (iv) 1 : 1.178: 1.524
12. The vander Waals equation for n moles of a real gas is :
(i) (p + ~) (Vb) =nRT (ii) (p + ~) (V nb) =nRT
(iii) (p + n:~) (V nb) = nRT (iV>(P + n:v2) (V nb) = nRT
True or False
State whether the following statements are true (T) or
false (F) ?
1. PV = ±mNi is an expression for the real gases.
2. The molecules of real gases have both volume and mutual attraction.
3; Pressure depends on the number of molecules and temperature.
4. The equation (1t + :2) (341 1) = 89 is known as the reduced equation of state.
5. The observed pressure of a real gas is less than the pressure of an ideal gas.
6. There are large number of particles in any sample of a gas for which the average
velocity must be zero, whereas the average velocity will always be final.
7. Gases which are difficult to liquefy have a low Boyle's temperature.
8. The vander Waals constant b is the actual volume of gas molecules.
9. Root mean square velocity of gas molecules is always greater than the average
velocity under similar conditions.
10. The ratio of the average molecular kinetic energy of CO2 to that of SF6 both at
300 K is one.
ANSWERS
Multiple Choice Questions
1. (i), 2. (i), 3. (ii), 4. (iii), 5. (iii), 6. (iv), 7. (iii), 8. (i), 9. (i),
10. (iii) 11. (ii) 12. (iii)
Fill in the Blanks
1. high 2. absolute temperature 3. high, low
4.652 5. (Vb) 6. vander Waals forces
7.586 K 8. directly 9. directly proportional
10. x 1l.lit2 atm mole2, lit mole 1
12. mutual attraction between gas molecules
True or False
1. (F) 2. (1) 3. (1) 4. (T) 5. (T) 6. (1)
7. (1) 8. (F) 9. (T) 10. (1)
.. 000
CHEMICAL AND PHASE EQUILIBRIUM
CHEMICAL EQUILIBRIUM
Problem 1: Exp1o.in 1o.w of mass action and equilibrium constant.
Guldberg and Waage (1867) found the effect of reacting substances on
a reversible reaction and gave a law known as the law of mass action.
According to this law,
"The rate at which a substance reacts is directly proportional to its
active mass and the rate ofa chemical reaction is proportional to the product
of the active masses of the reactants."
The term active mass of a reactant is the molecular concentration,
i.e., the number of gram moles per unit volume. It is expressed by enclosing
the formula of the substance within two square brackets, e.g., [H2], [HI] etc.
Consider a reversible reaction, A + B ~ C + D
According to the law of mass action,
Rate of forward reaction oc [A][B] = kJ [A][B]
where kJ is the velocity constant for the forward reaction.
Rate of backward reaction oc [C][D] = k2 [C][D]
where k2 is the velocity constant for the backward reaction.
At equilibrium: Rate of forward reaction = Rate of backward reaction
or kJ [A][B] = k2 [C][D]
[C][D] _~_
or [A][B]  k2  Kc ... (1)
where PA,PB,PC andpD represent the partial pressures of the respective con
stituents.
(103)
104 PHYSICAL CHEMISTRYI
Equations (1) and (2) are the mathematical forms for the law of mass
action.
In general, for a reaction
n 1A+n2B + ... ~ m 1C+m2D + '"
we can write,
K = [C]m. [D]mZ ...
C [A]n. [B ]n2 ..•
m. X m,x
Similarly, K = !....P"'C_P!....D/.!._ _
• ''
P n. X n2 X
PA PH •••
G=E+PVTS
On differentiation, we have,
dG =dE+PdV+ VdPSdTTdS ... (14)
From first law of thermodynamics, we have
dE=dQdW
If the work is only due to expansion, then dW = P dV
Hence, dE =dQ  P dV
or dQ=dE+PdV
or
(OG)
oP
=V
T
.... (17)
RT
For 1 mole of perfect gas, V = P
... (19)
llGA =
J~
PA
VdP= J~ dP=RT
RT
PA
J~ ~
P PA P
=RTlOgp'A IPA
Similarly, for the transfer of 1 mole of B from PB to P'B in the same
direction, the change in free energy is given by,
llGB = RT log P' B IPB
During the time A and B are transferred in one direction, 1 mole of C
and 1 mole of D are transferred isothermally and reversibly in the opposite
direction.
Thus, the free energy change for the transfer of 1 mole of C from
P' c to Pc is given by,
llGc=\RT logPc1p'c
For the transfer of 1 mole of D, we have,
llG D = RTlog PD Ip'D
CHEMICAL AND PHASE EaUILIBRIUM 109
or
=
P'A P'B P'c P'D
PAPB PCPD
, ,
PCPD PcPD
or   = ,, = Constant (Kp) ... (2)
PAPB PAPB
As the partial pressure is proportional to the molar concentration. equa
tion (2) becomes.
CC' CD [C] [DJ _
... (3)
CA' CB [AJ [BJ  K("
The equations (2) and (3) are different forms of law of mass action
which have been deduced thermodynamically.
is one of the forms of reaction isotherm deduced by van't Hoff (1885). If all
the partiaJpressure terms are replaced by concentration (c) terms, then equa
tion (3) can be written as,
I1G = RTlog K,.  RTLn loge. . .. (4)
Similarly, if partial pressure or concentration terms are replaced by mole
fraction (x) tenns, then equation (3) or (4) becomes at constant pressure,
I1G = RT log Kx  RT Ln log x, ... (5)
So, van't Hoff isotherm gives the increase offree energy change ac
companying the transfer ofreactants at any arbitrary concentration (or par
tial pressure) to products at any arbitrary concentration (or partial pressure).
Equations (4) and (5) are other fonns of van't Hoff isothenn. The
maximum work obtained is also given by equations (3), (4) and (5), and often
I1G is called the affinity of the reaction.
Rrdl~~Kp AH
dlogKp AH
or ... (5)
dT Rr
Equation (5) represents the variation of equilibrium constant with tem
perature at constant pressure. This equation is referred to as van't Hoff
reaction isochore (Greek: isochore = equal space), as it was first derived by
van't Hoff for a constant volume system. Since AN is the heat of reaction at
constant pressure, the name isochore is thus misleading. Therefore, equation
(5) is also called as van's Hoff equation.
An alternative form of equation (5) showing the variation of K(. with
temperature and involving the heat of reaction at constant volume is obtained
as follows:
We know that,
... (6)
where, An is the increase in the number of molecules in the gaseous reaction.
Taking logarithms of equation (6) and differentiating it with respect to
temperature, we have,
log Kp = log K(. + An log RT
d log Kp d log Kc + An
... (7)
dT dT T
Combining equations (5) and (7), we have
dlogKc AN An
dT = RrT'
d log Kc AN  An . RT
or
dT Rr
dlog Kc !J.E
or ... (8)
dT =Rr
[c.f. thermodynamics, AE = AH  An R71
where, !J.E is the increase of energy or heat of reaction at constant volume.
Equation (8) is another form of van't Hoff isochore or equation.
Integrated Form of van't Hoff Isochore
If AH remains constant over a range of temperature, then on integrating
equation (5), the result is,
CHEMICAL AND PHASE EQUILIBRIUM 113
till t1H
log., Kp =f Rr dT = RT + constant " .(9)
t1H
10gIO Kp =  2.303 RT + constant ... (10)
Equations (9), (10) and (11) are integrated forms of van't Hoff
isochore.
[II] Applications of van't Hoff Isochore
(i) To fmd the heat of reaction (MJ): It can be obtained by either
of the following two methods :
(a) If values of IOglO Kp are plotted agairist liT, we get nearly a
straight line. The slope of this line at a given point will be equal
to  MJI2.303R. The value of till can thus be measured by
measuring this slope.
(b) The second way to calculate t1H is from equation (11). Knowing
the equilibrium constants at two given temperatures, we may find
the value of t1H.
(ii) van't Hoff isochore is also applicable to find the heat of solution of
a substance from the temperature coefficient of the solubility, the heat of
dissociation of a weak electrolyte from the temperature coefficient of the
dissociation constant etc.
According to equation (5) the equilibrium constant of a gaseous reaction
increases with temperature, if till is positive. An increase in the equilibrium
constant means an increase in the proportion of the resultants, so that if heat
is absorbed in the reaction, an increase in temperature favours the formation
of the resultants. On considering the reverse case, if heat is evolved in the
reaction, an increase of temperature displaces the equilibrium in the direction
ofthe reactants. The behaviour is again in accordance with the LeChatelier's
principle.
be the freezing point and P will be the external pressure exerted on the system.
So, equation (3) can also be written in a reversed form as :
dT T~V
dP= MI ... (4)
If Vs and VL represent the molar volumes of the solid and the liquid
phases, respectively at temperature T and pressure P, then,
~V=VLVS
where, ~ V represents the increase in volume in transferring 1 mole from solid
to liquid phase, MI the amount of heat absorbed may be replaced by
~Hf' i.e., molar heat of fusion. So making these changes in equation (4), we
get the following Clapeyrons's equation.
dT T(VL  Vs)
... (5)
dP= Ml
f
(2) Liquidvapour Equilibrium
In this equilibrium, the increase in volume (~V) accompanying the
transfer of one mole of liquid to the vapour state will be equal to Vv  VL.
where Vv and VL represent the molar volumes of the vapour and liquid,
respectively.I1H may then be replaced by i1Hv, i.e., molar heat of vaporisa
tion.
From the above considerations, equation (4) becomes:
dT _ T(Vv  VL)
... (6)
dP  Mlv
It is a well known fact that the boiling point of a liquid is the temperature
at which its vapour pressure becomes equal to the external pressure. So,
equation (6) represents the variation of boiling point of a liquid with pressure
P. Thus equation (6) can also be written as :
dP Mlv

dT T(V v  VJ
... (7)
Equation (7) represents the rate of change of vapour pressure (P) of the
liquid with temperature.
Note: The volume measured at the same temperature and pressure,
i.e., Vvand VL are sometimes known as 'orthobaric volumes'.
[III] ClausiusClapeyron Equation
If the temperature of the liquid is not too near the critical point then we
can easily neglect the volume of the liquid (VL), compared to that of the vapour
(Vv). In such a case equation (7) reduces to equation (8) on replacing
Pby p. So,
... (8)
116 PHYSICAL CHEMISTRYI
fPI
Pz 1
d log P = T A ~ dT
TI
z
Rr
or log P2 = AHv Tz dT r
e PI R JTI T
P
log=k ( I Tc)

Pc T
where k is a constant which is equal to 3 for many substances. Hence in
reduced terms it can be put as,
log 1t = 2.3k (1  lie) ... (15)
Differentiating equation (?) with respect to e, we get,
dlog1t =2 3~
de . e2
NUMERICAL PROBLEMS
Problem 1: In the formation of silver chloride from its elements under
normal conditions, tJ.G is  26.3 k .. cals. and m is 30.3 k. caL per mole at
18°C. What is the corresponding entropy change?
Solution: From the following, we have equation
tJ.G = tJ.H  TtJ.S
or 26.3 = 30.3  291 x IlS
CHEMICAL AND PHASE EQUILIBRIUM 123
and
7 7
PeHp = 1; PeH 2 = 3 X 10 ; PeO! = 3/2 X 10
as one molecule of water yields one molecule of hydrogen and half a molecule
of oxygen.
For the reaction, 2H2 + O2 = 2H20
2
PeH,O 1
We have, K   :;=
14 7
p  P;H! x PeO!  9 X 10 x 1.5 X 10
1
==
1.35 X 1020
The change in free energy is given by,
AG =  RT loge Kp =  2.303 RT log 10 Kp
1
=  2.303 x 1.98 x 1000 log 20
1.35 x 10
=  2.303 x 1.98 x 1000 (log 1020 log 1.35)
=  2.303 X 1.98 X 1000 X 19.8697 = 90,610 cals.
:. Decrease in free energy of the system is 90,610 cals.
Problem 5 : The equilibrium constant of the reaction
2S02 + O2 ~ 2S03> at S28°C is 98.0 and at 680°C is 10.5. Find out the
heat of the reaction.
Solution: We know that,
loge Kp (I)  loge Kp (2) =  ~ UI ~)
where, Kp is the equilibrium constant and All is the heat of reaction.
log Kp (I) = 98.0 Kp (2) = 19.5 = 10.5
TI = 528 + 273 = 801 K T2 = 680 + 273 = 953 K
where, PI and P2 are the vapour pressures at temperature TI and T2, respec
tively and L. is the latent heat of evaporation/mole. It is given that:
PI =634 m.m.
P2 = 760 m.m.
TI = 95 + 273 = 368°K T2 = 100 + 273 = 273°K
or
or
PHASE EQUILIBRIUM
Problem 1 : Explain and illustrate the terms phase, component and degree
offreedom. (Meerut 2006, 2005)
In order to deal effectively with the heterogeneous equilibria, W.J. Gibbs (l873J
gave a generalised rule in the form of phase rule. Its utility was not immediately known
until several scientIsts like Ostwald. Roozehoom applied the rule to several well known
heterogeneous equilibria.
Before defining phase rule one must clearly understand the definitions of three
basic terms, which are frequently used In this connection. The three terms are :
(1) Phase, (2) Number of components, (3) Degree of freedom.
[I] Phase
A phase is defined as "any homogeneous, physically distinct part of
a system which is mechanically separable and bounded by a definite surface.
A phase can exist in either state of matter. viz .• solid. liquid or gas. A system
may consist of one phase or more than one phases.
CHEMICAL AND PHASE EQUILIBRIUM 127
Examples:
1. Pure substances: A pure substance (s, / or g) made of one chemical
species only has one phase, e.g., oxygen (02), ice (H20), alcohul
(C 2H50H) etc.
2. Mixture of gases: A mixture of gases, say H2, N2 and O2 contributes
one phase only as all gases mix freely to form a homogeneous mixture.
3. Miscible liquids: Two or more completely miscible liquids give a
uniform solution. e.g., a solution of water and ethanol has one liquid phase.
4. Nonmiscible liquids: A mixture of nonmiscible liquids forms as
many number of liquid phases as that of liquids, because on standing they
form separate layers, e.g., a mixture of water and chloroform forms two liquid
phases.
5. Aqueous solutions : An aqueous solution of a solid substance such
as NaCI is uniform throughout. So, there is only one liquid phase.
6. Mixture of solids : A mixture of two or more solid substances
contains as many phases. Each of these substances have different physical
and chemical properties and form a separate phase. Thus, a mixture of calcium
carbonate and calcium oxide has two solid phases.
7. In the dissociation of calcium carbonate there will be three phases,
viz., two solid phases (CaC03 and CaO) and one gaseous phase (C02),
8. In water system, there are three phases, viz., ice (solid), water (liquid)
and vapours (gas). Similarly, in sulphur system, there are four phases, viz.,
rhombic sulphur and monoclinic sulphur (solids), liquid sulphur (liquid) and
vapour sulphur (gas).
[II] Components
The number of components of a system is defined as, "the smallest num
ber of independently variable constituents by means of which the composi
tion of each phase can be represented by means of a chemical equation."
Constituents can either be elements or compounds. While writing the
chemical equations, we can use zero as well as negative quantities of the con
stituents, besides the positive ones (as is the convention).
Examples:
1. Water system: We know that water system consists of three phases,
viz., solid (ice), liquid (water) and gas (water vapours). Each of the three phases
is nothing else but water. Hence, all the three phases can be represented in terms
of the composition of only one constituent, water i.e., by the formula H20.
Ice (s) = H 20; Water (/) = H 20; Vapour (g) = H 20
So, water system is a one component system.
2. Dissociation of calcium carbonate: The case of dissociation of cal
cium carbonate is rather complicated. Its equilibrium can be represented as :
CaC0 3(s) ~ CaO(s) + CO2(g)
The composition of all the three phases can be expressed in terms of
either of the two components. Any two out of three substances can be chosen
as the two components. This is clearly understood as follows :
128 PHYSICAL CHEMISTRYI
Hence, in this case the two components are NH4CI and NH 3. If HCI is
present in excess over NH 3 , then the two components will be NH 4CI and HCI.
However, the system remains a two component system.
[III] Degree of Freedom or Variance
There are three variable factors, vi;::., temperature, pressure and concen
tration, on which the equilibrium of a system depends. In some cases, we
have to mention only one factor to define the system completely, sometimes
two or three. So, the degree of freedom (or variance) of a system is defined
as, the least number of variable factors such as temperature, pressure or
• concentration which must be specified so that the remaining variables are
fIXed automaticaUy and the system is completely defined.
System having degrees of freedom three. two, one or zero are known
as trivariant, bivariant, univariant (or monovariant) and nonvariant sys
tems, respectively.
Examples:
1. For icewatervapour system, F =0 : In the system, ice ~ water
~ vapour, the three phases coexist at the freezing point of water. As the
freezing temperature of water has a fixed value, the vapour pressure of water
also has a definite value. The system has two vaJiables (Tand P) and both these
are already fixed. So, the system is completely defined automatically and there
is no need to specify any variable. So, it has no degree of freedom, i.e., F = O.
2. For saturated NaCI solution, F = 1 : The saturated solution of
sodium chloride in equilibrium with solid NaCI and water vapour, i.e.,
NaCI(s) ~ NaCI (solution) ~ Water vapour
is completely defined if we specify temperature only. The other two variables,
i.e., composition of NaCI solution and vapour pressure have a definite value
at a fixed temperature. So, the system has one degree of freedom.
3. For a pure gas, F = 2 : For a sample of pure gas, PV = RT. If the
values of P and T are specified, volume (\I) can have only one definite value
or that the volume, i.e., third variable is fixed automatically. Any other sample
of the gas under the same pressure and temperature as specified above will
be identical with the first one. So, the system containing a pure gas has two
degrees of freedom.
Problem 2: (a) Define phase rule. (Meerut 2(04)
The mass of the phase does not enter into the equation. as it has no
effect on the state of equilibrium.
(II] Thermodynamic Derivation of Phase Rule
Consider a heterogeneous system in equilibrium consisting of C com
ponents distributed in P phases. The degree of freedom of the system is equal
to the number of independent variables which must be fixed arbitrarily to
define the system completely. The number of such variables is equal to the
total number of variables minus the number of variables which are defined
automatically because of the system being in equilibrium.
At C(quilibrium. each phase has the same temperature and pressure. so
there is ,one temperature variable and one pressure variable for the whole
system. So. these variables total two only. The number of composition (or
cOl\~ntration) variables. however. is much more. In order to define the
composition of each phase. it is necessary to mention (C  1) composition
yariables. because the composition of the remaining last component may be
. obtained by difference. Thus. for P phases, the total number of concentration
or composition variables will be P (C  1).
Total number of variables = P (C  1) + 1 + 1
for composition for temperature for pressure
= P (C 1) + 2
According to thermodynamics, when a heterogeneous system is in
equilibrium. at constant pressure and temperature, the chemical potential
(~) of any given component must be the same in every phase. Therefore. if
there is one component in three phases x. y and z and one of these phases.
say x is referred to as standard phase. then this fact may be represented in the
form of two equations :
~l (x) = ~l (y)
~l (x) = ~l (z)
So. for each component in equilibrium in three phases. two equations
are known. In general, therefore, for each component in P phases. (P  1)
equations are known. For C components, thus the number of equations or
concentration variables that are known from the conditions of equilibrium
are C (P  1). Since chemical potential is a function of pressure. temperature
and concentration. it means that each equation represents one concentration
variable.
Therefore. the number of unknown variables (which should be fixed)
or degree of freedom.
F = (Total number of variables)  (Number of concentration variables
which are already fixed)
or F=[P(Cl)+2][C(Pl)]
or F=CP+2
This equation is the phase rule as given bv Gibbs.
CHEMICAL AND PHASE EQUILIBRIUM 131
218
f atm.
~
~~ Ice
a..
4.58 Vapour
mm
Fig.l
Rhombic sulphur
(SR)
95.6"
~Monoclinic
(SM) J
120"
sulphur7 Liquid sulphur
(SL)
Changes
in colour
and viscosity
Vapour sulphur
(Sv) 444'
I:
..•• i
o
SR I$~ . ~~~
i r
I T.:~~mW~'~~O::~~)  ,I:
::;:;';;';;~;·;:;~i·;;;r~~·~1;;;;;;;;;;;;!
The significance of the features is discussed below.
(1) Curve AB : It is known as vapour pressure or sublimation curve
of Sib as it gives the vapour pressure of solid SR at different temperatures.
Two phases in equilibrium are SR and Sy. The system is, therefore, univariant
as,
F=CP+2
F=I2+2=1.
At B, SR changes reversibly into SM'
(2) Curve BC : It is known as vapour pressure or sublimation curve
of SM as it gives the vapour pressure of solid SM at different temperatures.
The two phases in equilibrium are SM and Sy.
The system is again univariant. At C, i.e., at 120°, SM changes into SL'
(3) Curve CD: It is known as vapour pressure curve ofSL, as it gives
the vapour pressure of SL at different temperatures. The two phases in equi
librium are SL and Sy. The system is univariant, as
F=CP+2=12+2=1.
i 136 PHYSICAL CHEMISTRYI
In water system, the three phases viz., ice (s), water (/) and vapours
(g) remain in equilibrium at a fixed temperature (O.0075°C) and fixed pressure
(4.58 mm). At no other temperature and pressure, all the three phases can
coexist in equilibrium. From phase rule equation (F = C  P + 2), we can also
show that value of F of the system is zero, i.e.,
F= 13 +2=0.
(2) Triple Point
Triple point is that point where all the three phases in a one component
system exist in equilibrium. At this point, both the variables, e.g., temperature
and pressure are fixed, i.e., they have definite values. Thus, triple point is a
nonvariant point, i.e., degree of freedom is zero. It is also clear from phase
rule equation i.e.,
t' = c  P + 2 = 1  3 + 2 = O.
The system at triple point is self defined. If any change is made in either
of the variable factors, one of the phases of the system disapppears. In water
system (figure I), 0 is the triple point where ice, liquid water and water
vapours exist in equilibrium. In sulphur system (figure 2), there are three
triple points namely B, C and E.
(3) Transition Point
It is defined as that temperature at which one allotropic form of a
substance is converted into another allotropic form of the same substance.
The point where this change occurs is called the transition point.
Example:
(i) At 95.6°C, rhombic sulphur is changed into monoclinic sulphur.
Below 95.6°C, rhombic sulphur can exist and above 95.6°C monoclinic
sulphur exist. Thus, 95.6°C is the transition temperature of sulphur (See
problem 3).
(ii) On cooling, white tin is converted into grey tin at 18°C (transition
temperature).
Problem 7 : What is a two component system and how it is graphically
represented? Define reduced phase rule equation and condensed state.
[I] Two Component System
A two component system is that system in which the composition of
each phase present in it can be represented in terms of two substituents,
e.g., leadsilver system, potassium iodidewater system etc.
Phase rule when applied to a two component system becomes
F=CP+2=2P+2=4P
Since the minimum number of phases in any system is one, it is evident
from the above equation that the maximum degree of freedom in a two
component system is three. Therefore, in addition to temperature and pres
sure, a third variable, namely composition, has also to be taken into account.
In order to represent such an eqUilibrium graphically, it is, therefore, necessary
to have three coordinate axes at right angles to one another. This will lead to
CHEMICAL AND PHASE EQUILIBRIUM 139
T P
C constant
t t
P
P T
I
C
: (a) (b)
T P
P constant T constant
t t
P P
c c
(c) (d)
:::::::::::: : '::':':':':':':':':':';'::}}}}i
d
:::::::
Fig. 3
.:.:.:. : :::::::::::::::::::::::::::::::::.:::::::::::::::::::::::
Unsaturated
solution
'X
I
1 I
Liquid + Solid silver
Solid
lead + Solid silver + Eutectic
Eutectic
F=CP+l=22+1=1.
3. Point C : The two curves AC and BC meet at a common point C.
Therefore, C gives conditions of temperature and composition under which
three phases, viz., solid silver, solid lead and solution coexist in equilibrium.
It is thus a nonvariant point as,
F = C  P + 1 = 2  3 + 1 = O.
CHEMICAL AND PHASE EQUILIBRIUM 141
,
Unsaturated solution x0
I B
i
~
~
Q)
a. SolidKI
E +
t! Solution
Ice + Solution
230
Ice + Eutectic Solid KI + Eutectic
0 52 100
Composition (% KI) _
PA° and PB° are the vapour pressures of the pure components A and B.
respectively and n term represents the number of moles.
If vapour behaves as an ideal gas then according to Dalton's law of
partial pressures, the total pressure (P) is given by
P=PA +PB
o
or P=XAPAo+XBPB ... (1)
Experiments show that Raoult's law is obeyed only approximately for
a number of binary solutions. It is obeyed perfectly only in case of ideal
solutions. So, a solution of two or more components is said to be ideal if it
obeys Raoult's law perfectly at all temperatures and concentrations.
Similar liquid pairs are generally found to form ideal solutions, e.g.,
binary mixtures of ethylene bromide and ethylene chloride, benzene and
toluene, nheptane and nhexane etc.
Vapour Pressures of Ideal Solutions
The vapour pressure of an ideal binary solution of two components A
and B is shown in Fig. 6. It is clear from the graph that the curve of the partial
pressure of each component against its mole fraction in the solution is a
straight line and the total vapour pressure of the solution for a given concen
Total ~
~, apOur pressur;
..... , ..... , e of solution P O.4PA + O.6PB
..... ,
..... ,oq P =X pO
, ..... :'1<1/ A A + XaPa
IJ ..... , IJre8s ,~
,
:.II ~.t'''''' lire , ,
, , "
I1IJ..qo'''''',~1 , ,
,
, ,
..... ... ...... ' "
,
,,."" ..."'........ ,
..... ,
sS\l{e " , 0
o\~" " ..... ,
.....
~&tU.&\ ~{~, , ~ , ::. 'J..o'YO ..... ,
..... ,
, , ", 0 ..... ,
, ..... ,
, , "
tration is equal to the sum of the partial vapour pressures of the two constit
uents. The total vapour pressure (P) of the solution is given by equation (1).
Thus, when the mole fraction of B is say 0.60, the total vapour pressure (P)
of the solution is given by
P = 0.4 PAc + 0.6PBo
aB =1
aA =1
< m
'0 '0
~ f
llC..______""t
XA = 1 Mole fraction =
XA 0
XB=O =
XB 1
CHEMICAL AND PHASE EQUILIBRiUM 147
three types :
Type I. Nonideal so
lutions of this type show small
deviations from ideal behavi
our and total pressure remains
always within the vapour
pressures of the pure compo ~
~ 400
nents, as shown in figure (8), f/)
Type II. Solutions of this type show large positive deviations and
the total vapour pressure curve rises to a maximum which is above the vapour
pressure of either of the two pure constituents A and B as shown in figure
(9). Mixture of ethyl alcohol and chloroform is a system which belongs to
this type.
Type III. Solutions of this type show large negative deviations and
the total vapour pressure curve dips to a minimum, for some of the concen
trations. The total vapour pressure of the mixture may be below the vapour
pressure of either of the two pure constituents as shown in figure (10). Mixture
of acetonechloroform is a system which belongs to this type.
~;'::":::':""\I
• 1: 1
I~ ::
;:::::.
0 0.2
A~ Mole tractionChlorotorm
0.4 0.6 0.8 ,.01
J:
:;:;:;:;:;:;:;~: ;: :;:;:;:;:;:;:;:;: :;:;: :;:;:;:;: : ~ !~: .~:~: : ;:;: : :;: :;:;:;: : : : : : : : : :~:;:;: : : : :
Vapour Pressure (or Boiling Point) Composition Curves
of Completely Miscible Binary Solutions
Consider a binary solution of two components A and B which are
completely miscible with one another. On heating under constant pressure, it
will boil at a temperature at which its total pressure becomes equal to the
atmospheric pressure. If PA and PB represent the partial pressures of the two
components A and B, then conditions for boiling is that
P=PA +PB
where, P is the atmospheric pressure.
CHEMICAL AND PHASE EQUILIBRIUM 149
T = Constant P = Constant
~A
::l
1ij
Q;
a.
Type I E
$ B
OJ
~
·0
co
0 1 0
Mole fraction of B Mole fraction of B
Composition (i) Composition (iv)
T=Constant P = Constant
C ~
~ ::l
::l
I/) ~A
I/) Q)
~ B a.
a. Type II E
$ B
OJ
~
·0
co
0 0
Mole fraction of B Mole fraction of B
Composition (ii) Composition (v)
T= Constant P= Constant
~ D
~ ::l
::l B ~
~ Q)
~ gA
a. Type III
SA $
OJ
8. ~ B
~ ·0
co
0
Mole fraction of B Mole fraction of B
Composition (iii) Composition (vi)
150 PHYSICAL CHEMISTRYI
100
B
90
U
0
e. 80
!~
e
~ 70
E
~
r 50
10 20 30 40 50 60 70 80 90 100
+ Percent A
152 PHYSICAL CHEMISTRYI
+ Composition
boiling mixture M.
Suppose a mix
ture of composition X
is distilled. The first
fraction distilled will have the composition indicated by Xl' Evidently, it is
richer in A. The composition ofthe residual liquid, thus shifts towards constant
boiling mixture M. As the distillation proceeds. the composition of the dis
tillate changes towards A and that of the residue towards M. Ultimately, a
distillate of pure A and a residue of constant boiling mixture M will be
obtained.
Similarly, a mixture of composition lying between Band M, say Y will
ultimately provide on distillation, a distillate of pure B and a residue of
constant boiling mixture M.
It is, therefore, evident thaI any binary solution of this type, on complete
fractional distillation, can be separated into a residue of composition M and
a distillate of either A or B depending upon whether the initial composition
lies between A and M or between Band M, respectively. Thus, it is not possible
to completely separate such a binary mixture into pure components A and B
on distillation.
CHEMICAL AND PHASE EQUILIBRIUM 153
The mixture with the maximum boiling point is called maximum boil
ing azeotrope and behaves as if it is a pure chemical compound of two
components, because it boils at a constant temperature and the composition
of the liquid and vapour is the same. But the azeotrope is not a chemical
compound, because its composition is not constant under conditions and rarely
corresponds to stoichiometric proportions.
Pure water and hydrogen chloride boil at 100° and 85°. while their
constant boiling mixture (azeotropic mixture) containing 20.25% of hydrogen
chloride boils at 108.5°, under a pressure of 1 atmosphere. If a solution
containing less than 20.25% of HCl is distilled, (i.e., between points A and
M), water will pass over as the distillate and the residue left behind in the
flask will consist of 20.25% solution of HCl in water. Thus, pure HCl can not
be obtained. Similarly, if a solution containing more than 20.25% HCl is
distilled, then pure HCl will pass over as distillate and the residue left behind
in the flask contain a mixture of the same constant composition, viz., 20.25%
HCl in water.
3. Solutions of type III. The boiling temperaturecomposition curve
for the liquid and vapour phases for such type of solutions is shown in
figure (15). The constant boiling mixture in this case has the minimum boiling
point, i.e., it is highly volatile.
Consider
distillation of compo
the m;:========z======mrm
sition represented by
X (fig. 15). Then the A
first fraction collected
will have the compo
sition X \. It will be
richer in the constant I
will become richer and richer in constant boiling mixture and pure B. respec
tively. Finally. the distillate will contain only the constant boiling mixture and
the residual liquid in the distillation flask will contain only B. There will be
no pure A in this case. If the mixture has the azeotropic composition (say Z),
it will distil unchanged.
In the system of waterethanol. the point M corresponds to a minimum
boiling temperature of78.13° and a composition of95.57% ethanol by weight.
If any solution of composition of pure water and 95.57% ethanol is distilled,
then we get a residue of pure water and a constant minimum boiling mixture
of 95.57% alcohol in the distillate. No pure ethanol can be recovered. On the
contrary. if a solution of composition between pure alcohol and 95.57% ethyl
alcohol is distilled. then we get a mixture containing 95.57% ethanol and pure
alcohol. No pure water will be recovered. .
Solubility of Partially Miscible Liquid Pairs
In the study of miscibility of partially miscible liquid pairs, the exterpal pressure i
kept constant and, therefore, the vapour phase is Ignored. The mutual solubilities ar(
epresented by means of temperaturecomposition diagram.
On the basis of mutual solubility of two liquids, there are three types of liquid pair
such as :
Type I: Tlwse pairs whose mutual miscibility increases with increasing temper
lature.
Type II: Those pairs whose mutual miscibility decreases with increasing tem
'perature.
Type Ill: Those pairs wlwse mutual miscibility both increases and decreases
with increasing temperature.
Problem 16: Discuss the theory of partially miscible liquid pairs with
special reference to :
(i) Phenolwater system
(ii) Triethylaminewater system
(iii) Nicotinewater system.
Define the upper and lower critical solution temperature. What is the
effect of impurities on them? (Meerut 2(04)
If we consider two liquids A and B and shake together, then some of A
dissolves in B. while some of B dissolves in A. We then have two saturated
solutionsone of A in B and the other of B in A. On increasing the temper
ature. the solubility of A increases in B and also drat of B in A. in this particular
case. As an example. we take the familiar phenolwater system.
[I] PhenolWater System
Phenol and water are partially mi'scible at ordinary temperature. When
we add phenol to water phenol gets dissolved in water. till its concentration
reaches 8%. The addition of more phenol will give rise to two liquid layers.
One layer will consist of water in phenol system and the other that of phenol
in water system. Such solutions of different compositions coexisting in
equilibrium with one another are known as conjugate solutions.
CHEMICAL AND PHASE EQUILIBRIUM 155
As the temperature is
raised, the solubility of phe
nol in water increases,
whereas that of water in Homogeneous
phenol also increases. Ulti
mately at a certain tempera ,,
ture, the two conjugate ,
solutions change into one :Tie line b
homogeneous solution. This t
temperature is known as
critical solution tempera I Heterogeneous
ture or consolute tempera 200 A : C
ture. The value of consolute
temperature for this system B
is 68.3°, and the composi
tion is 33% phenol and 67% o 203340 60 80 100
water. Above 68.3°, the two + Percent phenol
liquids are completely mis
cible in all proportions. The
variation of mutual solubil
ity of water and phenol with temperature is shown in fig. (16). The solubility
of phenol in water increases with rise of temperature along the curve AB,
while the solubility of water in phenol increases along CB. The two curves
do not intersect each other, but meet 'at a certain point B, known as C.S.T.
In between the area ABC, the system will be heterogeneous. If we
prepare a mixture of phenol and water of composition and temperature rep
resented by any point within the area ABC, it will separate into two liquid
layers or binary conjugate solutions. Any mixture of composition represented
by a point outside ABC will give a homogeneous solution.
At any fixed temperature say to, the composition of each layer is fixed
as shown by the points a and b, a gives the composition of the aqueous layer,
while b gives that of phenol layer. The line ab is known as tie line.
The amounts of the conjugate solution may be easily calculated. For example,
suppose we have a mixture of phenol and water, whose total composition is 50% phenol
at a temperature of 40°C. Then the data of the table of fig. (14) indicates that the two liquids
formed have the respective compositions 7.5% and 67% phenol. Let x be the weight of
aqueous layer in 100 g of the mixture and, therefore, (loox) g will be the weight of
phenolic layer. Then,
XU~)+(l00X>(I~ )=50
x=28.5
Therefore, lOOg of total mixture give rise to 28.5 g of aqueous layer and 71.5 g of
phenolic layer, or 285 x 0075 = 213 g of phenol is present in aqueous layer and
715 x 067 = 4790 g of phenol is present in the phenolic layer.
Other examples are (i) Wateraniline (167°), (ii) Benzeneaniline (59.so) (iii)Methyl
Alcoholcyclohexane (45.5°), (iv) BiZn (Metallic .\ystem) (85.0")
156 PHYSICAL CHEMISTRYI
DISTRIBUTION LAW
Problem 1 : State and explain Nernst's distribution law. What are the
limitations of this law? Give some important applications of distribution
law with special reference to extraction process.
(Meerut 2004, 20(H, Kanpur 2(05)
Or Define and discuss distribution law. (Meerut 2(05)
i.e.,
160 PHYSICAL CHEMISTRYI
w2 W KV W KV KV _W(~)2
 I KV + v  KV + v . KV + v  KV + v
Similarly, after nth extraction, the amount remained unextracted will
be given by,
W=W(K~~V) ...(9)
Since the quantity within the bracket is less than unity, (8) is smaller
than (9) and Wn will be smaller, the greater the value of n. Hence the efficiency
of extraction increases by increasing the number of extractions using only a
CHEMICAL AND PHASE EQUILIBRIUM 161
small amount of the extracting solvent each time. It must be remembered that
the value of K, the partition coefficient in equations (8) and (9) is that of the
substance between the solvent (A) in which the substance is already dissolved
and the solvent (B) which is used for extraction.
2. Determination of association: When a solvent is associated in
solvent 1 and exists as single molecules in solvent 2, the distribution law is
written as,
'vc; = K
Cz
where n = number of molecules which combine to form an associated mole
cule. Thus, knowing the values of C 1, Cz and K, we can calculate the value
ofn.
3. Determination of dissociation: Suppose a solute is dissociated in
aqueous solvent 1 and exists as single molecule in solvent 2. If a is the degree
of dissociation of the solute, the distribution law is written as :
A~X + Y
C2 (1  a) C2a C2 a
where, a is the degree of dissociation of solute A in solvent II.
According to modern distribution law.
K = Concentration of A in solvent I = C1
Concentration of A in solvent II C2 (1  a)
Such a case is observed in distribution of oxalic acid between water
and ether.
[III] Association of the solute in one of the solvents
Let A represents the normal
formula of the solute. It does not
associate in solvent I, but associates Solvent I
in solvent II to give molecules of No association
Conc. = C1
the type An (figure 20). Let C 1 be
the concentration of solute A in sol I~ Solvent II
vent I and C2 be its total concentra nA~A"
Association
tion in solvent II. occurs
In solvent II, the associated
. molecules exist in equilibrium with Total conc. <:2
single molecules, viz.,
An~nA
According to the law of mass
action,
CHEMICAL AND PHASE EaUILIBRIUM 163
or ... (1)
If the solute exists largely as associated molecules in solvent II, the
concentration of the associated molecules (An) may be taken to be equal to C2,
i.e.,
[An] = C2
Therefore, from equation (1), we get
[A] = constant x (C2)lIn = kC 2 l1n .
Applying the distribution law to similar molecular species, we have,
K = Concentration of A in solvent I
Concentration of A in solvent II
or K= Cj
k (C2)1I2
C1
or vi" = K . k =constant.
(C2)
Such a case is observed in the distribution of benzoic acid between
water and benzene.
NUMERICAL PROBLEMS
Problem 1 : The following data shows the distribution of phenol between
water and chloroform :
Concentration (cJ) in water 0.094 0.163 0.254
0.436
Concentration (C2) in chloroform 0.254 0.761 1.85
5.43
Calculate the partition coeffr.cient between water and chloroform. What
conclusions can be drawn from these results concerning the molecular
condition of phenol in chloroform layer?
Solution : Phenol in chloroform may be present either as normal
molecules or in the form of associated molecule», In the former case, Cl/c2
should be constant, whereas in the latter cl/c211n should be constant, where
n is the number of molecules of phenol associate to give a single associated
molecule.
The value of c 1/c2 in the four cases are given as follows:
CI
Now, the values of t= are given as follows :
VC2
. CI 0.094 CI 0 163
(I) :rc;=";(0.254) 0.1865, (ii);rc;=,,;(O.761) =0.1868,
(
... ) CI 0.254 0 1867 (.) CI 0.436 01870
11l rc;=";(l.85) . , IV rc;=";(5.43) . ,
Since c l /";C2 values are constant, therefore, phenol exists as double
molecules in chloroform.
Problem 2 : In the distribution ofsolute between water l ) and chloroform eC
(C2 ) the following data were obtained:
CI C2
0.163 0.761
0.436 5.43
What information do you gather regarding the molecular state of solute
in chloroform?
Solution: When the given solute exists as simple molecule in both
the phases, then C I /C 2 = K.
CI
C1 C2 =K
(In water) (In chloroform) C2
0.163 0.761 0.163 = 0 214
0.761 .
0.163
0.163 0.761 ~(0.761) = 0.1868
0.436
0.436 5.43 ~(5.43) = 0.1870
As the values of K are constant, the solute exists as double molecules
in chloroform layer.
ether. The partition coefficient of succinic acid between water and ether is
5.5. Succinic acid has normal molecular weight in both the solvents.
(Meerut 2005)
Solution: Let x g of succinic acid passes over into 50 c.c. of ether, then
the amount left unextracted in 100 c.c.water will be (5  x) g.
:. Concentration of solute dissolved in ether
=x g per 50 c.c.
Concentration of solute left in water
= (5  x) g per 100 c.c.
From the distribution law,
CI
K=
C2
= (5 x)/lOO
or 5 .5 x/50
or x =0.4166 g.
Amount of succinic acid extracted = 0.4166 g
Problem 4: At 20·C, S02 was permitted to distribute between 200 C.c. of
chloroform and 75 c.c. water. At equilibrium, the chloroform layer con
tained 0.14 mole ofS02 and water layer 0.05 mole. Calculate the distribution
coefficient of S02 between water and chloroform.
'
o ution
SI : Q~ mo Ies per c.c.
Cw = :ys
0.14 I
CCHCI3 = 200 mo es per c.c.
2:::: 50
(1 Xl)
100
or Xl =O;Sg
III second instalment: The amount of substance now left in aqueous
layer is 1~.5 g, i.e., 0.5 g. Consider by using next 50 c.c., X2 g of substance
passes over from 100 c.c. aqueous layer.
Then. concentration of substance dissolved in ether
= X2 g per 50 c.c.
Concentration of substance left in aqueous layer
= (0.5  x~ g per 100 c.c.
CHEMICAL AND PHASE EQUILIBRIUM 167
or 2= 50
(0.5 x2)
100
or X2 = 0.25 g
So, total amount of substance extracted in two instalments
= 0.5 + 0.25 = 0.75 g
Thus, it is clear that it is more advantageous to use 50 c.c. ether in two
instalments (as it extracts 0.75 g) rather than 100 c.c. 'in one instalment (as it
extracts only 0.66 g).
Problem 7: From the following data for the distribution of C~sCOOH
between water and benzene at 20·C :
(a) Show that C~sCOOH is associated as double molecules in benzene,
and
(b) Caku1ate the partition coefficient on the basis ofthis assumption. The
dissociation of C6H sCOOH in water may be neglected.
CHp = 0.015, 0.0195, 0.0289
Cell, = 0.242, 0.412, 0.970.
Solution: If benzoic acid remains normal in both the solvents, then,
K = CCH20 = 0.0 15 = 0.0619 ... (1)
C.H6 O. 24 2
= 0.0195
0.412
=0 .0461 ..,
(2)
= 0.0289
0.970
= 0.2980 ..,
(3)
Since the values of K are not constant, it is clear that benzoic acid does
not exist as normal molecules in both the solvents.
Suppose benzoic acid associates as double molecules in benzene, then
K = Cwater/'l/(Cbenzene)
(i) K = 0.0151"(0.242) =0.304
(ii) K = 0.0195/'1/(0.412) = 0.303
(iii) K =0.0289/"(0.970) =0.293
.. ff' . 0.304 + 0.303 + 0.293
S0, partitIon coe tClent = 3
=0.300
Problem 8 : 1 g of 12 is in 50 ml of CS2• 1000 ml of water is added into it.
Cakulate the amount of h extracted into water. Partition coe/ficiellt .?( h
in CS2 and H 20 is 200.
Solution : Suppose x g of h is extracted into water. Then, amount of
12 left behind in 50 m1 of CS 2 will be (1  x) g.
168 PHYSICAL CHEMISTRYI
~
Conc. of 10 In CSo
K ==  _._._':"
50
=:  
Conc. of 12 In H20 X
1000
~~
200==~0 or x == 0.0909 g
x
1000
So, amount of 12 extracted in waler == 0.0909 g
Problem 9 : At 25°C, the distribution coefficient of iodine between CCl4
and water is 85. If at 25°C, the solubility of iodine in water is 0.33 gllitre,
determine the solubility of iodine in CCI,Jo
Conc. orI z In CCI 4 Solubility Ofl2 in CCI 4 (S])
Solution: K     =
 Conc. of 12 in H 20 Solubility Ofl2 In H 20 (S2)
Sl
or 85=
0.33 g/litre
or Sl .= 85 x 0.33 g/litre
...: 28.05 g/Iitre
True or False
State whether the following statements are true (T) or
false (F) ?
1. P2 !1Hv
10glO PI = 2.303 R
(I 1"
T2  TI represents integrated formofClausiusClaperyon
equation.
2. Clapeyron equation can be applied to an equilibrium between any two phases
of the same substance.
CHEMICAL AND PHASE EQUILIBRIUM 171
3. van't Hoff isochore gives the temperature dependence of the vapour pressure of
a substance.
4. In the equilibrium N2 + 02 ~ 2NO, !l.H = x kJ, an increase of temperature will
shift the equilibrium towards the right.
[At' [Btl
5. In the reaction, nlA + n~B ~ mlC + m2 D, K~ = .
 , [C]m, [D]m 2
~. Nicotinewater has only one consolute temperature.
7. There is only triple point in sulphur system.
8. Henry's law is applicable to the solubility of H2 in water.
9. The eutectic point in KI  H 20 system is also known as cryohydric point.
10. In a two component system, three phases exist in equilibrium at the eutectic
point.
11. NaCI  H20 system belongs to a system in which the compound has an incon
gruent melting point.
12. For nonideal solutions, !l. Vmix is greater or less than zero.
13. HCl  H20 system has a minimum boiling azeotropic mixture.
14. Critical solution temperature does not change with pressure.
15. The two solvents should be soluble in each other, if distribution low is valid.
16. The solutions should be concentrated in distribution experiment.
17. The process of extraction of a solute is based on distribution law.
18. The degree of dissociation of NaCI can be calculated from distribution law
experiment.
19. If K = rc;;ICB,then solute exists as dimer in solvent B.
ANSWERS
Multiple Choice Questions
1. (d), 2. (a), 3. (b), 4. (d), 5. (c), 6. (c), 7. (d), 8. (d), 9. (a), 10. (c)
11. (a) 12. (c) 13. (b), 14. (b), 15. (c), 16. (c), 17. (c), 18. (b), 19. (d), 20. (a),
21. (c), 22. (c) 23. (d) 24. (c)
Fill in the Blanks
1. equilibrium constant 2. increases 3. Clapeyron
4. Kp = Kc (RT)'~N 5. Gibbs 6. four
7. one 8. MgZn2 9. F=CP+2
10. Jhree 11. one 12.303"C
13. decreases 14. associates 15. constant
16. Nemst 17. same
True or False
I. (T) 2. (T) 3. (F) 4. (T) 5. (F) 6. (T)
7. (T) 8. (F) 9. (F) 10. (F) II. (F) 12. (F)
13. (T) 14. (T) IS. (F) 16. (F) 17. (T) 18. (F)
19. (T)
000
(OllODIAl STATE
Problem 1 : Explain the terms colloidal state and colloidal solution. De
scribe various methods used in the preparation of colloidal solutions. Also
mention the different methods used for the purifICation of colloidal solu
tions. (Meerut 2002; Agra 2005,2003,2001; Kanpur 2005,2000)
DeIonised Water +
r Traces of Alkali
::;;E=~:ij:~t Spark
remove salt and then washed further when the precipitate of sulphur peptises
and forms a colloidal solution.
(ii) By exchange of solvent, i.e., by lowering of solubility : Colloidal
solution of a substance can be prepared by dissolving it in one solvent and
pouring this solution ill another solvent in which it is less soluble, e.g., a
sulphur or phosphorus sol can be prepared by adding their saturated alcoholic
solution in water.
(iii) Passing vapours of an element into a liquid: When the vapours
of a boiling element are passed through a liquid, condensation takes place
sometimes with the formation of a soluble sol, e.g., mercury sol can be
prepared by passing a stream of vapours from the boiling element into cold
water containing a suitable stabilising agent.
Purification of Colloidal Solutions
The colloidal solutions prepared by the above methods contain impurit
ies. These impurities must be removed in order to make the sol stable. This
is done by either of the following methods.
1. Dialysis : The purification of colloidal solution by this method is
based on the inability of the sol particles to pass through an animal membrane
or a parchment paper which allows only the molecules or the ions to pass
through. The vessel in which dialysis is carried out is known as dialyser
[Fig. (2)]. A dialyser consists of a special type of vessel open at both the
ends. To the lower end a membrane is stretched. This membrane allows only
the solvent and other molecules to pass through it, but it is impermeable to
the colloidal particles. The dialyser is then suspended in a larger vessel
~
'.
:e • ·e
.' R'
+ Ions
·.x·"1/~,"
~ e
~
Fresh
water.
e .~
~~
Fig. 2
176 PHYSICAL CHEMISTRYI
~n
DiaIYSiS bag
Olecule
Sol
particle " + '. +
~,'.\  I
Impure
colloidal (f) /"e  \ +
solution e ",/ Positiveion '. 
Gi......
e Water + Ions
+ Molecules
I& e
Anode
I ...e. , Cathode
'. Negative ion "
\ I
rD,
~ + •__ ...... ~~
' . . ....... I
Fresh
water. Watere
~
Fig. 3
The separation of the sol particles from the liquid medium and
electrolytes by filtration through an ultrafilter is called ultrafiltration. It is a
slow process. Gas pressure or suction is applied to speed it up. The colloidal
particles are left on the ultrafilter in the form of slime. The slime is then
stirred into fresh dispersion medium to get the pure sol. By using graded
ultrafiIters, the technique of ultrafiltration can be used to separate sol particles
of different sizes.
S.N. Characteristic
property Suspension Colloidal True solution
solution
I. Nature Heterogeneous Heterogeneous Homogeneous
2. Size range Particles are greater Particles are Particles are less
than 105 cms (or between 105 and than 107 ems (or
0.1 ~ Of 100 m~) 107 ems (or 0.1 i.! I m~) in diameter.
in diameter. to I m~) in
diameter.
3. Visibility Particles are viSIble Particles are Particles are not
under a generally VIsible visible even under
microscope or even under ultramicroscope.
with a naked eye. Ultramicroscope.
4. Diffusibility Do not diffuse Diffuse slowly Diffuse rapIdly
5. Filtrability Can be filtered Can be filtered Cannot be filtered
even by an through an animal
ordinary fi Iter paper. membrane, through
which the colloidal
particles do not
pass.
6. Molecular weight Low High Low
7. Osmotic High Low High
pressure
(o.P. oc M~W.J
8. Colour  Depends upon the Depends upon the
shape and size of nature of the ion.
the particle
the intensity of yellow colour of the sol does not increase further, the passing
of H 2S is stopped.
AS 20 3 + 3H2S ~ AS 2S 3 + 3H20
The excess of H 2S is removed either by boiling the colloidal solution
or by bubbling Hz through it, when a yellow sol of ASZS3 is obtained.
2. Ferric hydroxide sol: A colloidal solution of ferric hydroxide is
obtained by adding a freshly prepared saturated solution of ferric chloride (2
or 3 ml) drop by drop to 500 ml of boiling distilled water. Ferric chloride
hydrolyses to give a brown sol of ferric hydroxide sol.
FeCl3 + 3HzO ~ Pe(OHh + 3HCl
The hydrochloric acid formed and unhydrolysed ferric chloride are
separated by dialysis to get pure Fe (OH)3 sol.
3. Gold sol: A colloidal solution of gold (or purple of Cassius) is
obtained by reduction of auric chloride with stannous chloride or by HCHO.
2AuCl3 + 3SnCz ~ 2Au + 3SnCl 4
2AuCl3 + 3HCHO + 3H20 ~ 2Au + 2HCOOH + 6HCl
A trace of KZC03 is added to neutralise the acid formed whose presence
renders the sol unstable.
4. Sulphur sol : A colloidal solution of sulphur is obtained by the
oxidation of HzS with dil. HN0 3 or sulphurous acid.
3H zS + 2HN03 ~ 2NO + 4H 20 + 3S
2H2S + H ZS03 ~ 3HzO + 3S
The colloidal solution of sulphur so formed is treated with saturated
salt solution when sulphur is precipitated. It is filtered, washed with water to
remove salt and then washed further when the precipitate of sulphur peptises
and forms a colloidal solution.
5. Silicic acid sol: It is obtained by adding a solution of sodium silicate
to a solution of 4N HCI with constant stirring till the acid is in excess. The
mixture is diluted to about twice its volume and then dialysed against running
water till it is free from HC!.
6. Carbon sol : It is obtained by rubbing lamp black with water in
presence of little protective colloid like gum arabic, when a colloidal solution
of carbon (Indian ink) is formed.
7. Iodine sol: It is prepared by oxidising hydroiodic acid with iodic
acid, when a purple colloidal solution of iodine is obtained.
5HI + HI0 3 = 3HzO + 312
8. Mastic sol: It is a resin type hydrophilic colloid. Its colloidal solution
is obtained when it is dispersed in only pure distilled water. As such it carries
a very little charge, but when dispersed in acidic solution and alkaline solution,
a positively charged and negatively charged sol, respectively is obtained.
180 PHYSICAL CHEMISTRYI
L Prepared by direct mixing wIth Not prepared by direct mixing with the
dispersion medium, medium,
8 Reversible. Irreversible.
2. Peptisation
See problem 1.
3. Dialysis
See problem 1.
4. Ultramicroscope
Zsigmondy and Siedentopf (1903) devised ultramicroscope to study
Tyndall effect. It consists of an ordinary microscope with a special arrange
ment for focussing a beam of light. The light from an arc lamp S is allowed
to pass through a projection lens Ll and objective lens L z and focussed into
a vessel containing a colloidal solution C. The light scattered from colloidal
particles now enters the microscope M placed at right angle to the path of
light. The colloidal particles look as pin points of light. We do not see the
colloidal particles in this ultramicroscope but see the light scattered by them.
As each particle can be detected as 'spot' of light, therefore, slit ultra
microscope helps to determine the number of particles in a definite volume.
The great value of the slit consists in the ability by its use to suction off a
portion of the fluid which is being examined. Zsigmondy (1912) devised an
immersion ultramicroscope, which was used with strongly coloured liquids.
In it, illumination objective and microscope objective are brought as close as
possible, and the liquid to be investigated can be used as a drop between the
two lenses.
The ultramicroscope does not give any information regarding the shape
and size of colloidal particles.
5. Tyndall Effect
When a strong beam of light is passed through a true solution, it cannot
be seen unless the eye is kept directly in the path of light, but when the same
beam of light is passed through a sol and viewed at right angles, the path of
the light becomes illuminated. This is due to the fact that sol particles absorb
182 PHYSICAL CHEMISTRYI
f!F""""":;':'"''''''''''''''''''''''''''''''''''''''''"""""""""""""""""""""""","','""""""'""""""""""'''''''''''''''''''''\!J
M Microscope
Knife
I
Objective Projection edge Projection
lens lens slit lens
o C:>Arc
o ~Iight
;;};;;:;;:~~::~~;i':;;':!
light energy and then emit it in all directions in space. This scattering of light
illuminates the path of the beam in the colloidal solution. The phenomenon
of the scattering of light by the colloid particles is called Tyndall effect. The
illuminated beam or cone formed (figure 5) by the scattering of light by the
sol particles is often referred to as Tyndall beam or Tyndall cone.
If the sol particles are large enough, the sol may even appear turbid in
ordinary light. as a result of Tyndall scattering. As ions or solute molecules
are too small to scatter light, the beam of light passing through a true solution
is not visible when viewed from the side. So, Tyndall effect can be used to
distinguish a colloidal solution from a true solution.
The blue colour of sky, hazy illumination of the light beam from the
film projector in a smoke filled theatre or light beams from the headlights
of a car on a dusty road are common examples of Tyndall effect.
M~SCOpeO
A
Halo
around
sol particle
*
~ • ~
scattered
View under
microscope
',',
'.'
COLLODIAL STATE 183
6. Brownian Motion
R. Brown (1827) observed that
• .• ?"""".".,."'
• . """"'."'., ,""""'·'·'·"'··""?·ll::
when a sol is examined with an ultrami
croscope, the suspended particles are :::,
~ ~
equalise each other. As the size is reduced, the probability of unequal bom
bardment rapidly increases, whereby the Brownian movement becomes more
and more violent.
Applications and Importance
(i) Confirmation of kinetic theory: It is a direct demonstration of
ceaseless motion of molecules as pictured by kinetic theory of motion.
(ii) Determination of Avogadro's number: With the help of ultrami
croscope, the number of particles in a given mass of the gas can be counted
and the Avogradro's number, i.e., the number of molecules in one mole of
gas can be calculated.
(iii) In stabiliSing colloidal solution: The zigzag motion prevents the
184 PHYSICAL CHEMISTRYI
Applications of Electrophoresis
(i) In determining the charge : The nature of the cha~ge on a
colloidal particle can be ascertained by its migration in an electriC field.
(ii) In electrodeposition of rubber: The latex obtained from the sap
of certain trees is an emulsion of negatively charged rubber particles dispersed
in water. This can be deposited on any substance which is made the anode
during electrolysis.
(iii) In the removal of colloidal smoke from outgoing gases : The
removal of negatively charged carbon particles from smoke can be done by
passing the smoke between positively charged metal electrodes. The principle
has been utilised in the construction of Cottrell precipitator.
COLLODIAL STATE 185
:.
~ 0
Hydrophilic   H2 0 Hydrophobic
sol particle :. _ : Layer _ _ sol particle
~j j
.0
 
Dehydrating
,s,ub,s,ta_nce,,_~..
0 Sol particle
If no protective colloid is present in the gold sol, it will turn from red
to blue. The smaller the gold number of a protective colloid, the greater is its
protective power.
Gold Number
Colloid Gold number
Casein 0.1
Gelatin O.OOSO.OI
Dextrin 6.20
Starch (potato) 2S.0
Colloidal Si02 oc
Thus, starch has a high gold number, which shows that it is an ineffective
protective colloid, while gelatin has a small gold number and is thus an
effective protective colloid.
(problem : Gold number of starch is 25. Calculate its amount to be added intd
100 ml of gold sol so that it is not coagulated in presence of 10 ml of 10%
NaCI solution.
Solution : Goid number of starch is 25 means 25 mg of starch IS added to
prevent coagulation of 10 ml of gold sol by I ml of 10% NaCI solution. For 100 ml
of gold sol, 250 mg of starch is needed to prevent coagulation by 1 ml of 10% NaCI
solution. But for 10 ml of 10% NaCI solution, only 251~ 1 mg or 25 mg of starch is
I[Cquired.
13. Stability of lyophobic Colloids
Preventing coagulation of a colloidal solution by any means is known
as stabilising the colloid. Bancroft (1915) gave the position with regard to
stability. He said that 'allY substance may be blVugllt into a colloidal state,
plVvided the particlt:.s of the dispersed phase are so small that the Brownian
movement keeps the particles suspended and plVvided the coagulation ofllie
particles is prevented by a suitable sUlface film '.
It was observed that lyophobic sols are stable due to their electric charge.
As most of the lyophobic sols are prepared by preferential adsorption of ions,
the mutual repulsion of particles is responsible for their stability. The sols
become unstable, as soon as they are robbed off their charge. However, in
case of lyophilic sols, the stability is due to electric charges as weIl as
solvationa phenomenon in which the colloid particle is surrounded by a
thin film of the solvent. The layer of the solvent forms an envelope around
each colloidal particle and thus preforms an envelope around each colloidal
particle and thus prevents the particles from coming together. Groups like
COLLODIAL STATE 189
radium. It is seen that the coagulation effect of the rays is independent of the
sign of the colloid. Lal and Ganguly (1930) studied the coagulating influence
of UV light on sols of AgI, Au, Ag, V205' Th(OHh, As 2S3 etc.
14. Isoelectric Point
Isoelectric point is that point at which the concentration of the positi ve
ions in solution becomes equal to that of the negative ions. Similarly, in case
of colloidal solutions, a sol may be positively charged in presence of an acid,
due to the preferential adsorption of H+ ions. On the contrary, a sol may be
negatively charged in presence of an alkali, due to the preferential adsorption
of OH ions. However, there must be an intermediate H+ ion concentration
at which the colloidal particles are neither positively nor negatively charged.
Hence, the isoelectric point in case of colloidal solution, is that point at which
the colloidal solutions have no charge at all.
IsoeleclI"ic point plays an important part in the stabilization of a sol.
The stability of a sol is due to the presence of zeta potential (see subsequent
pages) which is zero at the isoelectric point. At this point, the colloidal
particles will not move towards any electrode under the influence of electric
field. Hardy said that at isoelectric point, the colloidal particles are electro
phoretically inert. Isoelectric point also occurs in protein sols. A protein
solution is amphoteric. In acidic medium, a protein sol is positively charged,
while in an alkaline medium, it is negatively charged. At a certain point or at
a certain pH, the particles will have equal positive and negative charges.
Different protein sols have different isoelectric points, e.g., isoelectric point
for a gelatin sol occurs at pH == 4.7. Below pH 4.7, the colloidal particles of
gelatin move towards the cathode, while at pH greater than 4.7 the particles
move towards the anode.
15. Emulsions and Characteristics
Emulsions are liquidliquid colloidal systems. In other words, an emul
sion may be defined as a dispersion of finely divided liquid droplets in
another liquid.
Generally, one of the two liquids is water and the other. which is
immiscible is designated as oil. Either liquid can constitute the dispersed
phase. .
Types of Emulsions : There are two kinds of emulsions:
(i) Water in oil type: In it water is the dispersed phase and oil acts
as dispersion medium, e.g., butter etc. It is designated by WIO or wino.
(ii) Oil in water type: In it oil particles form the dispersed phase and
water is the dispersion medium, e.g., milk, vanishing creams etc. It is desig
nated by O/W or oinw.
Tests for Types of Emulsion : The two types of emulsions can be
experimentally identified in a number of ways, which are as follows:
COLLODIAL STATE 191
~~~~!i~;~~~~~~~=~~~:=::~~~~~~~~
:::::.:::::::
  B:: =:=
   :=:=:=
:~;:~~~~~~~~
t
~~~~~~~~~:~;~~
:~
Polar head
~~~~:~:~;:=~
~:~~:~:~~~;~~
Hydrocarbon
tail
    
~~~~~~+:~.:::~ ~::._:N~:~~~~
  
   
  

 

 
   Water
Fig. 11
ions are given by the ionisation of hydrogen sulphide, which is present in
traces. Similarly, the negative charge on metal sol particles obtained by
Bredig's method is due to the preferential adsorption of hydroxyl ions given
by the traces of alkali present. The positive charge on sol of Fe(OH)3 prepared
by the hydrolysis of ferric chloride is due to the preferential adsorption of
ferric ions on the surface of the particles. The ferric ions are obtained by the
dissociation of ferric chloride present in traces in the sol.
!·.:ii·················++:··:~:::~::~··;;:::=I~'i
:.I..
+:+
+·  + +•
I
I

+ +
+ +::::
::::
','
+
+·
+ +I
•
+
+ + :}
+:+
+ + +
I
I
I

+
+ +
.,.....,
I
I
, 
......... \
+
y
IY"'e.~u~::~:+! .'.
" .
.'.
i;;;;;;~~. ;~ . '··;1
(iv) Articles ofdaily use: Milk which is a complete food is an emulsion
of oil in water (OfW) type stabilised by casein. Butter is an emulsion of water
dispersed in fat (O/W) type. Fruit juice is a colloidal system having juice
dispersed in the solid tissue of the fruit. Ice cream is ice particles dispersed
in cream.
(v) Formation of deltas: The river water contains colloidal particles
of sand and clay which carry negative charge. The sea water on the other
IY;':::::::::;;:~~:::::::+
• ~=~<~~ ~
.'.
~
e J:
~
~ R~~ j
~ 4
: : :· i:~:~ ~ :~·: :;~;~; :;: ~:; :i~: ~ ~;~;:~:~;i~.~;~;·.·.~ ~.:·.·.~.~.~:;~i:;·:.;:i.:i~:i:~:; ;·i.~. ;~;t;i;·. ;:·:l:·~.: ~ !
hand, contains positive ions such as Na+, Mg2+, Ca:!+. As the river water meets
sea water, these ions coagulate the sand or clay particles which are precipitate<!
as delta [Fig. (14)].
\
202 PHYSICAL CHEMISTRYI
!
COLLODIAL STATE 203
(viii) Dyeing: Cotton, silk and wool are all colloidal in nature having
a gel structure. The dyestuffs include a number of substances having different
propertIes; their degree of dispersion is colloidal.
preCip~~i:n~O:;ok:~~ a:;s7e: " .: " :; : :." ' ':' ' .:.;' ' ': : ~.::;.:"':':.~::""':":::"'~'.,"':''''''''~'''''D:'u's:t~fr"":e"":~'"'·::··"":;:=.i.:
in which carbon particles are dis :::: gases
persed in air carrying a negative ):
charge. In large industrial cities '. ir
:yO~~:~h~:sa~~:;a~i~~:sc;::~ i:l!
ent in it are very injurious to ::::
human health. So, to remove car :::
bon particles, use is made of ::
'Cottrell electrical precipitator' ..:.::'
[Fig. (15)] in which the smoke is '.' Point electrode
made to pass through a positively.;.;
Plate electrode
charged anode in the chimney,
when carbon particles settle f Gases carrying
dust or smoke
down. According to a modern :;::
]~
I •
anisotropic and anisometric or both, so that the electrical charge and water
of hydration, if any, are unequally distributed. When the correct amount of
electrolyte is added to reduce the zeta potential to a sufficient extent, the
particles tend to coalesce, but owing to their shape they can form a stable gel
only if correctly oriented. The extent of the surfaces of the particle in contact
is probably limited, and as a consequence. any stress will tend to reduce this
and destroy the gel structure. It is interesting to note in connection with this
theory, that nearly all thixotropic sols show marked streaming double refrac
tion, so that the particles are probably anisotropic or anisometric.
(iii) Three dimensional theory: This theory is based on the hypothesis
of three dimensional gel structure as already described before. It is supposed
that when a gel is thixotropic, shaking is only sufficient to break the cross
linking, thus reforming the sol. The particles would then be linear, thus
accounting for the double refraction of now suggested in the second theory.
[II] Influence of Foreign Substances on Thixotropy
Thixotropic gelation may be considered as a form of nocculation and
is sensitive to all kinds of additions. The time of solidification (1) is strongly
dependent on the concentration (c) of the electrolyte, as seen in the empirical
equation given by Schalek and Szegvari (1923),
log T=A  B.c
It has been shown that thixotropic gelation is a slow coagulation. Time
of soliditication is also changed with a change in the pH of the solution as
mentioned by Freundlich. It is seen that alcohol promotes the thixotropic
gelation and after evaporating the alcohol. the sol returns to the gel state.
[III] Influence of Temperature on Thixotropy
As seen from Schalek and Szegvari's experiments, the increase of
temperature will decrease the time of solidification.
[IV] Applications of Thixotropy
The phenomenon of thixotropy has found several applications in bio
logical fields, technology and in articles of daily use. Protoplasm has thixo
tropic properties. Myosin sols are known to form strongly thixotropic gels,
which might indicate that thixotropy has a significance for muscular action.
Most of the quicksands are thixotropic in nature. The appl ication of thixotropy
i!> much used in drilling muds used in drilling oil wells. Drilling muds always
contain a certain amount of plastic clays responsible for its thixotropy. Paints,
varnishes and printing inks are all thixotropic in nature. A paint having a
greater time of solidification is considered to be its good property. A suspen
sion of graphite in a mineral oil shows a thixotropic gelation.
208 PHYSICAL CHEMISTRYI
True or False
State whether the following statements are true (T) or
false (F) ?
1. The lower the gold number, the better is the protective power of a protective
colloid.
2. Lyophobic sols are irreversible in nature.
3. The process of passing a precipitate into colloidal solution on adding an elec
trolyte is called electrophoresis (Meerut 2(02)
4. Colloidal system is biphasic in nature.
5. Colloidal solutions exhibit Brownian motion.
6. The soap may be considered as a surfactant.
7. Blood carries a positive charge.
8. Lyophilic colloids can act as protective colloids.
210 PHYSICAL CHEMISTRYI
9. The role of an emulsifier is to increase the surface tension between the two
phases.
10. Elastic gels are reversible in nature.
11. Gum arabic is a hydrophobic colloid. (Meerut 2(03)
12. The colour of a colloidal solution depends on the shape and size of the particles.
13. Avogadro's number can be determined with the help of Brownian motion.
14. Out of NaCI, BaCI 2, AICI 3 solutions, the coagUlating power of NaCI is maxi
mum for coagulating a As 2S3 sol.
15. The difference in potential between the fixed and diffuse layers of an electrical
double layer is called streaming potential.
16. Boot polish is not a colloidal system. (Meerut 2(01)
ANSWERS
Multiple Choice Questions
1. (b), 2. (d), 3. (b), 4. (b), 5. (b), 6. (d), 7. (a), 8. (d), 9. (c),
10. (d) 11. (a) 12. (d) 13. (c), 14. (a), 15. (d), 16. (d). 17. (d). 18. (c),
19. (d). 20. (b),
• DOD
CHEMICAL KINETICS &CATALYSIS
1. CHEMICAL KINETICS
Problem 1: (a) Define and discuss the following terms:
(i) Rate of chemical reaction
(ii) Velocity coeffICient
(iii) Molecularity of a reaction
(iv) Order of reaction (Meerut 2007, 2006, 2005)
Or, Write a note on order and molecularity of reactions.
(b) What is the difference between molecularity and order of reac
tion?
(Meerut 2002 2004. 2000)
(C) Explain why reactions of higher orders are rare?
(d) What are the factors which affect reaction rates? (Meerut 2003)
(211)
212 PHYSICAL CHEMISTRYI
1 d [N20 5 ] 1 d [N02 ] d [0 2]
"2 dt =+4" dt =+~
[II] Velocity Coefficient
Consider the following reaction :
A + B ~ Products
If a and b are the initial concentrations of the reactants A and B and if x
be the number of moles of each reactant undergoing reaction after time t, then
the concentrations A and B after time t will be (a  x) and (b  x) respectively.
According to the law of mass action, the reaction rate (dxldt) is given by
dx oc (a  x)(b  x) or dx = k (a  x) (b  x)
dt dt
where, k is a constant known as velocity constant, rate constant, velocity
coefficient or specific reaction rate. It is characteristic of the reaction.
If (a x) = 1 and (b x) = 1, then
k=: = Rate of reaction
So, velocity coefficient is defined as, the rate of reaction under con
ditions when the molecular concentration of each reactant is unity.
[III] Molecularity of Reaction
It is defined as, the total number of molecules of all the reactants
taking part in a chemical reaction as represented by a simple equation.
Examples. (i) Inversion of cane sugar (Molecularity = 2)
H+ ions
C 12H 220 11 + H 20 7 C6H 120 6 + C 6H I2 0 6
(ii) Dissociation of ammonia (Molecularity = 2)
2NH3 ~ N2 + 3H2
(iii) In general, for a reaction, nlA + 1I2B ~ 113C + 11l2D the molec
ularity will be nl + 112'
So, reactions having molecularity 1,2, 3 etc., are known as unimolecu
lar, bimolecular, trimolecular reactions, respectively.
[IV] Order of Reaction
Reactions are generally classified on the basis of their order of reaction.
It is defined as,
'The total number ofreacting molecules whose concentration changes
during the chemical reaction. '
In other words, it is also defined as,
'The total number of reacting molecules whose concentration deter
mines the rate of reaction '.
(a) If A ~ Products and (dxldt) = k [A], then
Order of reaction = 1
CHEMICAL KINETICS & CATALYSIS 213
H+ ions
CH3COOC 2H 5 + H 20   7 CH300H + C 2H 50H
Thus, often molecularity of a reaction coincides with its order, but the
two need not be always identical. The molecularity must be an integral value,
but the order of reaction may be zero, whole number or even fractional.
Whereas molecularity can be given on the basis of some proposed theoretical
mechanism so as to satisfy the experimental findings, the order of reaction
can be obtained from experimental results.
For complex reactions, occurring in steps, the molecularity of each step
will be different, while the order of reaction will be determined by the slowest
step.
TableI. Difference between order of reaction and molecularity
Molecularity Order of reaction
l. It is equal to the number of molecules of J. It is equal to the sum of the powers of the
reactants which take part in a single step molar concentrations of the reactants mJhe
chemical reaction. rate expression.
2. It is a theoretical concept which depends 2. It is an expermientally determined quantity
on the rate determining step in the reaction which is obtained from the rate for the
mechanism. overall reaction.
214 PHYSICAL CHEMISTRYI
On integration, we get
Sunlight
H2 (g) + CI 2 (g) t 2HCI (g)
Problem 3: What is a half order reaction? Derive rate equation for it
and discuss its characteristic.
[I] Half Order Reaction
A reaction in which the reaction rate depends on half power of concen
tration of a reactant is known as half order reactioll, i.e .•
A ~ Products
. cbc
.. ReactIOn rate. dt = k [A] 112
[II] Rate Equation for Half Order Reaction
Consider the reaction.
A ~Products
(Initial COliC.) a
(COliC. at time t) (ax)
dx
 _ k (a _ x )112
dt
dx
or l/~ = k dt
(a  x) ~
On integrating,
dx 112 =fkdt
f (a x)
1 112
or (ax) ===kt+I ... (1)
2
where I = integration constant.
When t = O. x = O. so
! a 112 = I
2
Putting the value of J in equation (1). we get.
 2"1 (a  x)
112
= kt  2"1 a 112
... (2)
Equation (2) is the required rate equation for a half order reaction.
CHEMICAL KINETICS & CATALYSIS 217
: :::: k {A] = k (a  x)
The concentration of water does not change during the course of the
reaction, as it is taken in excess.
Similarly, for the reaction,
H+
C 12H 220 Il + H20 ~ C6 H 120 6 + C6H 120 6,
the rate of reaction is given by
dx
dt = k [C12H220111
are added to freeze the equilibrium. It is titrated against N/1O NaOH, using
phenolphthalein as an indicator. Similarly, 5 ml of the reaction mixture is with
drawn after say 5,10,20,30 minutes and also at the end of 24 hours, when the
reaction is supposed to be complete. The solution is then titrated as usual.
Suppose the volumes of standard NaOH solution required for the neu
tralisation of 5 ml of the reaction mixture, at the start of the reaction, after
time t and at the end of the reaction, are VO,VI and V~, respectively. Then
x, the amount of acetic acid formed after time t is proportional to
(VI  Yo), while a, the initial concentration of the ester is proportional to
(V~  Yo). Thus, (a  x), the concentration of the ester left behind unreacted
after time t is proportional to (V~  yo)  (VI  yo) or (V~  VI)' SubstitutIng
the values of a and (a  x) in the first order rate equation,
k  2.303 10 _a_
 t g,oax
we get, k  2.303 log V~  Vo
 t 10 V~  VI
or dx = k dt
(a _x)2
where k is the velocity constant.
In order to get the value of k, we integrate the above expression, i.e.,
dx 2 =fkdt
f (a x)
1
or =kt+1
(a x)
(I = integration constant) ... (1)
* It is assumed that the concentration of the substance which is taken in excess does not
appreciably change during the course of the reaction.
222 PHYSICAL CHEMISTRYI
1=1..
a
Substitutmg the value of 1 in equation (1). we get
1=kt+1..
ax a
1 1
or =kt
ax a
or k=1..[_l _1..]
t ax a
or _1_ [_1___1_]
(a  b) (b x) (a x)
dx = k dt .. ,(3)
1
or (a _ b) [loge (b  x) + lo~ (a  x)] = kt + 1 ... (4)
(l = Integration constant)
When t = 0, x = 0, therefore, from (4),
1 1 a
(ab) [Iogeb + loge a] =1 or 1 = (a _ b) loge b
Substituting the value of 1 in equation (4), we get
_1_ (ax) _ _1_ ~
(ab) loge (bx) kt+ (ab) loge b
or
1 _! ~ __1_
112 k . a (aI2)  k . a
1
or tl/2 oc
a
i.e., the time is inversely proportional to the initial concentration of the
reactant.
Problem 9: What are third order reactions? Derive the rate expressions
and d~cuss their characteristics. Give examples of third order reactions.
CHEMICAL KINETICS & CATALYSIS 225
or dx kdt
(a _x)3
On integration, we get
f(a :t X
)3 =f k dt
1
=kt+1 ... (1)
2 (a _x)2
where 1 = integration constant.
When t =0, x =0, we then have
_1_=1
2a 2
Substituting the value of 1 in equation (1), we get
1 1
=2 = kt +2
2(a x) 2a
1
kt=,.
2(a xi  2a2
=1. [a 2 (a  X)2] =! x (2a  x)
2 a2 (a _x)2 2 a2(a _x)2
dx
dt = k(a  x) (b  x) (c  x)
dx
ill =k&
(a  x) (b  x) (c  x)
Breaking into partial fractions, we get
dx + dx + dx =k~
~~~~~~ ~~~~~~ ~~~~~~
On integrating, we have
On integrating, we get
k= 1 [2x
(2b  a) + In b (a  2x)]
t (2b  a)2 a (a  2x) a (b  x)
i.e.,
CHEMICAL KINETICS & CATALYSIS 227
dx =k [At =k(a  xt
dt
On integrating, within the boundary conditions, t =0, x =0, we get
fo x dx =fl kdt
(axr 0
or
[(nI)(:_X)(nI)I~: =k[t(~
or _1_[ "I
(nI) (aJx)(nl) a(nl) 
_I_]kt
\"
or k ~ I. [ 1(
t(nl) (ax)n
I) ( 1 I)]
a n
... (1)
This equation is applicable for all orders except when n = 1, because
when n = 1, n  1 = 0.
So,
k 0 t
1 [
X0
1
(a _ x)'  :0 j
..,
228 PHYSICAL CHEMISTRYI
1 [2(n
= k(nl) a(nI)  a(nI)
I) 1]
1 [2(n I)
= k(nl) a(nI)  a(nI)
1]
= 1 [2(nl) _ 1]
k(nl)a(nI)
(2(nI)1) 1
t1l2 = k(n _ 1) . a(n  1) .•• (2)
1
or t 112 = Constant X (i1=1)
a
1
or t 112 oc (i1=1)
a
Problem 11: Discuss the methods employed in determining the order of
a reaction. (Meerut 2005, 2001)
There are several methods to determine the order of a reaction.
[I] Integration Method (Hit and Trial Method)
In this method, the initial concentrations of all reactants are determined.
The concentration of the reacting substances is then determined by analysing
the reaction mixture at different intervals of time. The different values of a
and x are then substituted in rate expressions of the first, second and third
order reactions. The order of reaction is given by that equation which gives
a nearly constant value of k. This method, therefore, involves the trial of one
equation after another till the correct one is found. This method is extensively
used for simpler reactions.
CHEMICAL KINETICS & CATALYSIS 229
or
or
or
* It is assumed that the concentration of the substance which IS taken in excess does not
appreciably change during the course of the reaction.
230 PHYSICAL CHEMISTRYI
( '5 :;.:
.... ...... ·o~
U1<_~.,{?_i'._O"_~0_1. q;:_0~
:::: ~ ~
I
.... (ax)_
: : :. ~========~:
The various values of dxl dt (Yaxis) are plotted against the correspond
ing concentrations (a  x) on Xaxis as shown in figure (2). If we get a straight
line, the reaction is of the first order. In case, a straight line is obtained by
plotting dxl dt and (a  x)2 or (a  x)3, the reaction is of second or third order,
respectively.
Problem 12: Di1icuss the energy of activation and temperature coeffi
cient. (Meerut 2000)
Or Di1icuss the effect of temperature on reaction velocity in the light of
Arrhenius theory. How the energy of activation of a chemical reaction can
be determined experimentally?
[I] Temperature Coefficient
See problem 1 (d).
[II] Energy of Activation
Arrhenius (1889) put forward the hypothesis that all the molecules of
a reactant do oot take part in the chemical reaction. It is only a certain number
of molecules known as active molecules that may take part in the reaction.
CHEMICAL KINETICS & CATALYSIS 231
The molecules not capable of taking part in the reaction are known as passive
molecules.
On raising the temperature, the equilibrium between active and passive
molecules is supposed to shift over rapidly, so that not only we have an
increased collision frequency, but still more, we have a largely increased
number of active molecules ready to take part in the reaction. The equilibrium
is represented as
Mpassive ~ Mactive
K = [M active]
a [M passive)
dlogek EI E
In general, dT = Rr or d log e k = 
Rr . dT ... (4)
On integration, we get
E
loge k =  RT + constant ... (5)
k' IT' £
fk
I
dlogek=
T
I
ry
RJ'
dT
k? £ ( 1 1)
or 10glO k~ = 2.303 R TI  Tz ... (8)
10 kT + 10 = 20,000 X 10 "" 1
ge kT 2 X (300)2
.....
::::
Activation Activation
~{ energy energy of
.... >. reverse process
:I w
~.
!
E1 Reactants '
A ~~.   t_     t __
AE = Heat of reaction
~L~~B
Products }~
p~~g~~~.S reacti~n.
!li:·\:::................................................................ .. Of =. .. . . . . . . . . .....
);l..;.
:.:::::::::::::::::::::::::::::::::::::::::::::::::::::\::::::::::;::::::::::.:.::: :/.:.: ::::. ~i~..3.. :::::::;::::::::::;:::::::::::::}}::::::::::;::::::::::::::::::::::::::::::::::::::\\:
In the above case, the reactants are shown to possess a total energy
higher than the products. So, according to the law of conservation of energy.
there will be a release of energy, i.e., heat will be evolved. The reaction is
exothermic and the amount of heat evolved gives the heat of reaction. This
release of energy is shown by llE. Evidently, llE = EI  E2, where EI is the
normal energy of the reactants and E2 that of the products. In this case, llE
is negative as energy is released and not absorbed. An exothermic reaction
has thus a lower activation energy or a faster rate of reaction. Now, consider
the reverse reaction (B ~ A). Since the energy (E2) of molecules of B is
less than the energy (E)) of A, as shown in the figure, energy will be absorbed
and not released, i.e., the reverse reaction will be endothermic. An endother
mic reaction has always a greater activation energy and hence has a slow~r
rate of reaction than the opposing reaction.
* k3
Second stage: A ~ Products
The first stage involves collision of reacting molecules forming a few
activated molecules represented by A*, with a velocity cQnstant k b after which
timelag occurs. During this timelag the activated molecules lose their excess
energy and revert to the original state, with a velocity constant k 2•
Alternatively, the activated molecules may decompose into products,
with a velocity constant k 3•
2
Rate of activation =k l [AJ
Rate of deactivation = k2 [A*] [A]
236 PHYSICAL CHEMISTRYI
Rate of decomposition = k3 [A *]
According to the stationary or steady state principle, whenever a
shortlived reaction intermediate occurs in a system, its rate of formation can
be taken as equal to its rate of disappearance. Applying this principle, we have
kl [A]2 = k2 [A'] [A] + k3 [A']
or = [A·] {k2 [A] + k3}
, kl [A]2
[A ] = k2 [A] + k3
Since the rate of reaction is proportional to the concentration of actI
vated molecules, we can, therefore, write that,
... (2)
Activated complex
EI of reactants
E2
E2 = Activation ",",2rn'",':'"
of products
E
E' 
Products
Reaction path_
(ii) The reactant molecules are changed into an energy rich interme
diate called activated complex or transition state (fig. 4).
(iii) The activated complex may be formed by some loose association
or bonding of reactant molecules with necessary rearrangement
of valence bonds and energy. If it is a unimolecular reaction, the
reactant molecule may produce the activated complex by rear
rangement of atoms and redistribution of energy.
(iv) The activated complex, though unstable, has a transient existence.
It is treated formally as a definite molecule with an independent
entity. The activated complex remains in equilibrium with the
reactants and its potential energy is maximum. Finally, the acti
vated complex decomposes into products.
(v) The activation energy of reaction in the light of this theory, is the
additional energy which the reacting molecules must acquire to
form the activated complex.
Thermodynamic or Mathematical Treatment of Transition
State Theory
Consider a bimolecular reaction between reactants A and B. According
to transition state theory,
238 PHYSICAL CHEMISTRYI
A + B ~ x* ~ Products
Reactants Acti vated
complex
The equilibrium constant (K) for the formation of activated complex
is,
_ [x*]
K  [A] [B] or [X*] = K [A] [B] ... (1)
or (:. E=AJt)
or
or
The steric factor P is thus related to entropy of activation.
(ii) In collision theory, no account is taken of the internal motions of
the reactant molecules, whereas in transition state theory, account is taken of
the internal degrees of freedom of reactant molecules and the changes these
undergo on reaction.
(iii) The concept of entropy of activation in transition state theory is
very useful for qualitative purposes. Thus. for bimolecular processes, this is
an advantage over the colliSIOn theory.
240 PHYSICAL CHEMISTRYI
ReactIOn rate = 
o 1 d[A]
 d[B]
 = I  
III dt 112 dt
CHEMICAL KINETICS & CATALYSIS 241
=+ ~ d [C] =+ ~ d [D]
n3 dt n4 dt
. IS:
SoI. The fiIrst ord er rate expressIon . k 2.303
=  Iog
a
t ax
The amount of KMn04 is proportional to the amount of H 20:! present,
so the volume ofKMn04 used at zero time corresponds to initial concentration
(a) and the volume used after time t, corresponds to (a  x) at that time.
Inserting these values in the above equation, we get
2.303 I a 2.303 I ro  r~
k =   oglo= o g  
t ax t rtr~
where ro, rl and r~ are the optical rotations at the start of the reaction, after
time t and at the completion of reaction, respectively. Inserting the values in
the above equation, we get
The constancy in the value of k shows that the reaction is of the first
order.
Ex. 3: Decomposition of diazobenzene chloride was foUowed at constant
temperature by measuring the volume of nitrogen evolved at different times.
The data is given below:
t (min) o 20 so 70
o 1 10 2S 33 162
2.303 I
k 70 = m 162 2.303 I 162 000326
ogiO 162 _ 33 = m oglo 129 =.
·1
mm
CHEMICAL KINETICS & CATALYSIS 243
The constancy in the values of k shows that the reaction is of the first
order. The specific rate constant, k is thus given by :
1 al 1 a2
or loglo 085 =  . IOglO 04
20 . al t2 . a2
For half the reaction, let the time taken be fl, then X == 0.5a.
2.303 a
.. k ==   loglO 05
tl a . a
0.693
or fl ==k ... (i)
Suppose the time taken for 99.9% of the reaction is t2' then
x=0.999a.
2.303 a
k == t2 loglO a  0999 ... (ii)
. a
244 PHYSICAL CHEMISTRYI
[A] [B)
I 2.0 2.0 2.0 x 103
II 4.0 2.0 4.0 x 103
III 6.0 2.0 6.0 x 103
IV 2.0 4.0 2.0 x 103
V 2.0 6.0 2.0 x 103
VI 2.8 8.0 2.0 x 103
Give:
(a) Order of reaction with respect to A (Meerut 2007)
(b) Order of reaction with respect to B (Meerut 2007)
(c) Overall order of reaction (Meerut 2007)
(d) Rate law equation
(e) Rate constant
Sol. (a) According to sets I, II, III, we can infer that order of reaction
with respect to A {when [B] is kept constant} will be 1.
(b) According to sets IV, V, VI, we can infer that order of reaction
with respect to B {when [A] is kept constant} will be O.
(c) Overall order of reaction = 1 + 0 = 1.
(d) The rate law equation will be
dt = k [AJ
dx ... (.)
1
(e) From set I, we can substitute the values of dx/dt and [AJ in
equation (i). Therefore,
3
20 X 103 = k x 2.0 or
k = 2.0 X 10 = 103 s1
2.0
Ex. 7: 1 ml of methyl acetate was added to 20 ml of N/20 HCI at 2SOC. 2
ml of the reaction mixture was withdrawn at different times and titrated
with a standard alkali.
Time (millutes)
ml qf alkali used
.
CHEMICAL KINETICS & CATALYSIS 245
_ log (84/84)
.. n  1 + log (79/707) 1 + 0 or n = 1
For second set:
_ log (84/84) _ _ _
n  1 + log (07.5/79)  1 + 0  lor n  1
:. Order of reaction = 1.
Ex. 10 : The timefor half change (t)for a gaseous reaction was measured
for various initial pressures (p). The following data were obtained :
Ex. 12: The following data were obtained for a gaseous reaction :
Initial pressure (mm) 200 300 400
k2
or kl =2= 2k3 ,.. (i)
or 5.5 5 3
x = 1.055 = .21
:. 5.213% of the initial concentration had changed into product.
Ex. 15: An acid solution of sucrose was hydrolysed to the extent of 57%
after 66 min. Assuming the reaction to be of first order, calculate the time
taken for 75% hydrolysis.
or t = 108.4 min.
Ex. 16: For a first order reaction, the rate constant is found to be 7.0
x 107 at 'PC and 9 x 104 at 5'PC. Calculate the energy of activation and
its specific reaction rate at 12'PC.
, k2 E
Sol. ,We know that, log k; = 2.303 R T\  T2
[1 1]
where, E=activation emvgy, T\=273+7=280K,k l =7xl07,
4
T2 = 273 + 57 = 330 K, k2 = 9 X 10 .
So, from equation (8), we get
7
log (9 x 104)  log (7 x 10 ) = 2.303 ! 1.987 [ 2!0  3~0 ]
E [330280]
= 2.303 x 1.987 280 x 330
4 7 Ex50
or log (9 x 10 ) log (7 x 10 ) = 2.303 x 1.987 x 280 x 330
  Ex50
or 4.9542 7.8451 = 2.303 x 1.987 x 280 x 330
26290 [1 1]
log k400  log k280 = 2.303 x 1.987 280  400
E [781  556J
=2.303 x 1.987 557 x 781
3.954 x 102
log 7X 2.303 X 1.987 X 556 x 781
E= 3.517 x 10
225
= 44610 cal/mole.
where, A = frequency factor.
Hence, 3.517 x 107 = A.e44610/1.987 x 556
7 44610
or log 3.517 x 10 = log A  1.987 x 556
or  6.4538 = log A  40.2910 or log A = 33.8372
or A = 6.874 X 1034•
Ex. 18: In the saponification of ethyl acetate by sodium hydroxide using
equal concentrations the progress of the reaction was foUowed by titrating
25 ml of the reaction mixture at regular intervals against standard acid.
The foUowing data were obtained:
Time (min) 0 15 25 35
Volume of acid used (ml) 16 6.13 4.32 3.41
1 (16  4.32)
k25 = 25' 00069 . I I
16 x 4.32 =. mm cons
k=!. x
t a (a  x)
CHEMICAL KINETICS & CATALYSIS 251
..
k=.!.. x
t a (a  x)
When the reaction is 20% complete, x = 0.2a
k=_l_. 0.2a 1. 0.2a _ __
.. 500 a (a  0.2 a) 500 a X 0.8a 2000 a
Suppose it takes t\ seonds for the reaction to go to 60% completion.
N k =1. . 0.6a _ 1 0.6a =1. . l
ow, tl a (a  0.6a) t 2 · a X OAa tJ 2a
1 .
 3 =
or
tl 2a 2000a
t) = 3000 sec.
Ex.4: A second order reaction with two reactants is started with O.IM
concentrations of each reactant. It is 20% completed in 500 seco~ds. How
long will it take the reaction to go to 70% completion?
For a second order reaction when the concentrations are equal, we have
k=.!.. x
t a (a  x)
For 20% completion: a =0.1, x= 0.2 X 0.1 =0.02; t =500
k = _1_ X 0.02 =_1_ X 0.02 =_I_
.. 500 0.1 (0.1  0.02) 500 0.1 x 0.01 200
For 60% completion: a = 1; x =0.6 X 0.1 = 0.06; t = ?
k=! X 0.:.::.06=_
.. t 0.1 (0.1  0.06)
1 1 0.06
or =x
200 t 0.1  0.04
200 x 0.06
or t =Q.l X 0.04 =3000 seconds.
2. CATALYSIS
Problem 1. Define catalyst and catalysis. Mention the types and classifi
cation of catalysis. Discuss the characteristics of catalytic reactions.
[I] Catalyst and CatalysiS
Berzelius (1835) found that the speed of a number of reactions is in
creased due to the presence of a small quantity of a foreign substance. He also
252 PHYSICAL CHEMISTRYI
found that these substances remain chemically unchanged at the end of the
reaction. He termed these substances as catalysts and the phenomenon itself is
known as catalysis. A familiar example is that of the decomposition of
KCI03 . The decomposition of KCl0 3 is very slow even at high temperature,
but a small quantity ofMn02 increases the rate of decomposition to a very great
extent and Mn02 remains chemically unchanged at the end of the reaction.
2KCl03 + [Mn02] ~ 2KCl + 302 + [Mn02]
But later on it was observed that there are certain substances which can
retard the rate of a chemical reaction. Hence. Ostwald defined that.
"A catalyst is a substance which influences the speed of a 'chemical
reaction without itself undergoing any chemical change at the end of the
reaction. "
Catalysis is mainly divided into two types. viz .• homogeneous catalysis
and heterogeneous catalysis.
[A] Homogeneous Catalysis
When the catalyst is present in the same phase as that ofthe reactants,
the phenomenon is known as homogeneous catalysis.
(a) Examples of homogeneous catalysis in gas phase
(i) Oxidation of sulphur dioxide (S02) to sulphur trioxide (S03) with
nitric oxide (NO) as catalyst.
2S02 + O2 + [NO] ~ 2S03 + [NO]
Gas Gas Gas Gas
I
2H20 2 ~ 2H20 +02
(ii) Hydrolysis of cane sugar in aqueous solution in the presence of
mineral acid as catalyst.
Catalyst
Other reactions are :
Mn°2
(ii) 2KCI03 ~) 2KCI + 302
PtorNO
(iv) 2S02 + O2 ) 2S03
(b) Negative CMaJysis: When the foreign substance retards the
speed of a chemical reaction, it is known as a negative catalyst and the
phenomenon is known as negative catalysis. The following are examples of
this type.
(i) Decomposition of hydrogen peroxide
H,P04
2H20 2 ~ 2H20 + O 2
(ii) Oxidation of chloroform
C,H,OH
4CHCl3 + 302 ) 4COCI 2 + 2Cl2 + 2H20

(iii) Tetraethyllead as antiknock
When tetraethyllead. Pb(C2H5)4 is added to petrol. it retards the too
rapid or explosive combustion of the fuel which is responsible for the working
of the engine.
Explanation of Negative Catalysis
The mechanism of negative catalysis could be different for different
reactions, e.g .•
(1) By poisoning a catalyst. A negative catalyst may work by poi
soning a catalyst which already happens to be present in the reaction mixture.
CHEMICAL KINETICS & CATALYSIS 255
For example, the traces of alkali dissolved from the glass of the container,
catalyse the decomposition of hydrogen peroxide (H20 2). However, the ad
dition of an acid would destroy the alkali catalyst and thus prevents decom
position.
(2) By breaking a chain reaction. In some cases, negative catalysts
are believed to operate by breaking the chain of reactions. For example, the
combination of H2 and C1 2, which is a chain reaction, is negatively catalysed
by nitrogen trichloride (NCI 3).
Cl2 ~ Cl'+Cl'
Free radicals
A+B ~ C+D
is shown in fig. (6). In the begin
ning, the concentrations of A and
B are maximum and so the rate of
forward reaction is maximum. As
the time passes, the rate of the re
action decreases till the equilib
rium is established. For the reverse Equilibrium
reaction, the initial concentrations
of C and D are zero and the rate of
reaction is lowest. As the time
passes, the rate of reaction in
creases till the equilibrium is estab Time.
lished. Similar curves of the rates
of reactions with the catalyst show
that the rates of the forward reac :::::: time required for ih:e equilibrium ::::::
tion and the reverse reaction are )t. . . . '.' . . . . . . .~. ~. ~~~~.~~~~:......................... mm
changed equally but the equilib
rium is established in a much shorter time.
For example, in the Haber's process for ammonia,
Fe
N2 + 3H2
2NH3 ~
the reaction is very slow. In the presence of the catalyst, the equilibrium is
reached much earlier but the percentage yield remains unchanged. The iron
catalyst decreases the time to attain equilibrium but cannot change the per
centage yield.
Energy considerations also show that the final state of equilibrium
cannot be changed by the catalyst. Suppose the catalyst accelerates the for
ward reaction more than the reverse reaction. This will shift the equilibrium
point, which cannot happen without the supply of energy to the system. But
a catalyst unchanged in mass and~composition at the end of the reaction,
cannot supply the required energy.
Problem 2. Write notes on the following:
(a) Catalytic promoters (b) Catalytic poisons
(A) Catalytic Promoters
The activity of a catalyst can often be increased by the addition of a
small quantity of a second material. This second substance is either not a
catalyst itself for the reaction or it may be a feeble catalyst.
A substance which, though itself not a catalyst, promotes the activity
of a catalyst is called a promoter or an activator.
[I] Examples of Promoters
(i) In some reactions, mixtures of catalysts are used to obtain the
maximum catalytic efficiency. For example, in the synthesis of methanol
CHEMICAL KINETICS & CATALYSIS 259
(CH 30H) from carbon monoxide and hydrogen, a mixture of zinc oxide and
chromium oxide is used as a catalyst.
Peak
&
~i~i~i~i~i \~
1'% I I
NiNiNi
I I I I I I I I
NiNiNiNiNi NiNiNi .;,:
I I I I I I I I ~
NiNiNiNiNi NiNiNi U
I I I I I I I I I
NiNiNiNiNi NiNiNiNiNi
I I I I I I I I I I
IF''''''''·'''''''''''·''''''·'·'''·''·'·'·'·'·'''·'·'·'·'·''·"'·'·'·'·'·"·'·'·"~;?;S,:"·""""""·'·'·"·"'·'·""""·''''11
~ Distance between
catalyst particles ~
/f I"
:.:.. .:.:.:.:.:.:.:.:. .:.:.:.:.:.:. :..:.:.:.:.:.:.:.: . catalyst makes the reaction go faster? ':::':::::::": ;.:.: :::::
::::::::::::::::::::::::::::.........................................................................................................................................................................::}}»}:.:;.:
(a) Examples of Catalytic Poisoning
(1) The platinum catalyst used in the oxidation of hydrogen is poisoned
by carbon monoxide.
Pt
2H2 + O2 +) 2H20
Poisoned
by CO
(2) The platinum catalyst used in the oxidation of sulphur dioxide
(contact process) is poisoned by arsenic oxide (AsP3)'
Pt
2S0 2 + O2 +) 2S03
Poisoned
by AS20 3
(3) The iron catalyst used in the synthesis of ammonia (Haber's process)
is poisoned by H 2S.
Fe
N2 + 3H2 +) 2NH3
o o o
II
c,
II
c
II
,
, , , , ,c,
, , ,, ,, , , ,,
Fe + H2S ~ FeS+H2
Problem 3. Discuss the theories of catalysis and also mention the indus
trial applications of catalysts.
[I] Theories of Catalysis
Many theories have been put forward to explain the catalytic activity
of catalyst. A few important theories are given below :
1. Intermediate Compound Formation Theory
According to this theory, a catalyst first combines with one of the
reactants to form an intermediate compound of activity greater than that of
the reactants. This intermediate compound then reacts with another reactant
fufurm the product and so gives back the catalyst. If A and B are two reactants
and C is a catalyst, then according to this theory. .
A+C~ AC
AC+B ~ AB+C
A+B+[C] ~ AB+[C]
This theory can be fully explained by the following examples :
(1) In the oxidation of S02 by air, NO which acts as a catalyst, first
combines with oxygen to form N0 2 (intermediate compound) which oxidises
S02 and gives back nitric oxide.
2NO + O2 ~ 2N0 2
[S02 + N0 2 ~ S03 + NO] x 2
2S0 2 + O2 + [2NO] ~ 2S03 + [2NO]
(2) In the formation of ether from alcohol, H2S04 which is used as
catalyst first forms an intermediate compound C2H sHS0 4 .
C2HsOH + H2S04 ~ C2HsHS0 4 + HP
C 2HsHS04 + C2HsOH ~ C2HsOC2HS + H2S04
262 PHYSICAL CHEMISTRYI
!!;,t;i;;;i·;;~;:;?~~;.·~~~~~~?~~;:::~t··g::.····.·
The mechanism of contact catalysis may vary in details, depending on
the nature of the reactants. Consider the example of hydrogenation of ethene
in presence of nickel. In this casse, ethene adds hydrogen in the presence of
nickel as a catalyst to yield ethane.
H H
I I
_N_i.....:(c_a_ta....;ly'st')~) HCCH
I I
H H
Ethene gas Ethane (gas)
il'::"""'''''''''~'''''''''''''''''''''''''''''''''''''''''M""""""""'·":'~
j H/r:I"H HH/CC"HH
)~ @@ I
:'.! Step 3 Step 4 \
2NO + 02 ~ 2N02
4N02 + 2H20 + 02 ~ 4HN03
4. Manufacture of hydrogen by Bosch's Ferric oxide + Cr203 (as a promoter) at a
process temp. of 400°600°C.
(CO + Hz) + H20 ~ C02 + H20
Water gas
5. Manufacture of methyl alcohol from ZnO + Cr203 (as a promoter). 200 atms.
water gas pressure and temp of 450°C.
CO+H2 +H2 ~ CH30H
Water gas
(2) Like inorganic catalysts they cannot disturb the final state of equi
librium of a reversible reaction.
(3) They are highly specific in nature, i.e., one catalyst cannot catalyse
more than one reaction.
(4) They are highly specific to temperature. The optimum temperature
of their activity is 35°C to 40°C. They are deactivated at 70°C.
(5) Their activity is increased in the presence of certain substances,
known as coenzymes.
(6) A small quantity of enzyme catalyst is sufficient for a large change.
(7) They are destroyed by U.v. rays.
(8) Their efficiency is decreased in presence of electrolytes.
[II] Examples of Enzyme Catalysis
The following are some examples of biochemical or enzyme catalysis.
(1) Manufacture of ethyl alcohol from cane sugar
Glucose Fructose
Zymase
C6H120 6 ) 2C 2H50H + 2C0 2
(2) Manufacture of acetic acid from ethyl alcohol
Maltase
C 12H220 U + H20 ~) 2C6H l2 0 6
Maltose Glucose
J
CHEMICAL KINETICS & CATALYSIS 267
where kl' k2' k3 are the rate constants for the respective reactions.
The rate of formation of the complex ES is, evidently given by the
following equation,
... (1)
where [E], [S] and [ES] represent molar concentrations of the free enzyme,
substrate and the complex, i.e., bound or reacted enzyme, respectively.
Now [E] cannot be experimentally measured. The equilibruim between
the free and bound enzyme is given by the enzyme conservation equation,
i.e.,
[E]o = [E] + [ES]
d [ES] = 0
dt
268 PHYSICAL CHEMISTRYI
. 1
Maxlmum rate, 2 Vmax
(ii) If [S] is very large as compared to Km, the factor Km/[S] will be
negligibly small as compared to unity and so the rate of formation
of P, i.e., d [P]/dt will be independent of the concentration [S].
In other words, the reaction will be of zero order with respect to
S (Fig. 13).
(iii) If [S] is very small or very large, the reaction remains of the first
order with respect to the total concentration, [E]o of the enzyme.
Problems 5. mite a short note on acidbase catalysis. (Meerut. 2007)
As a result of the work of Bronsted, Lowry and others, it has become
evident in recent years that a variety of atomic, molecular and ionic species
are capable of catalysing chemical reactions. For some processes, hydrogen
ions appear to be effective, while other reactions are catalysed by hydroxyl
ions, cations of weak bases, anions of weak acids, undissociated molecules
of acids and bases etc. This general acid catalysis involves cases where all
acids act as catalysts, while general base catalysis refers to processes
catalysed by bases of all kinds. In some cases, both acids and bases are
effective, while in others a particular species is effective. General acidbase
catalysis is illustrated by mutarotation of glucose, which is catalysed by
hydrogen, hydroxyl and complex ions, as well as by the acids and bases,
though the most effective catalyst is the hydrogen ion.
270 PHYSICAL CHEMISTRYI
H H
15. If the plot of 10glO [A] against time is a straight line with a negative slope, the
order of reaction is :
(i) 0 (ii) 1 (iii) 2 (iv) 3
16. In the hydrogenation of oils the catalyst used is :
(i) Iron (ii) Platinum
(iii) Nickel (iv) Molybdenum
17. The effect of a catalyst in a chemical reaction is to change the:
(i) Activation energy (ii) Equilibrium concentration
(iii) Heat of reaction (iv) Final product
18. The catalyst used in the contact process of sulphuric acid manufacture is :
(i) Oxides of nitrogen (ii) Nickel
(iii) Vanadium pentoxide (iv) Manganese dioxide
19. Which of the following is used as a contact catalyst?
(i) Boron (ii) Germanium
(iii) Nickel (iv) U~anium
20. Which of the following statements is universally correct?
(i) A catalyst remains unchanged at the end of the reaction
(ii) A catalyst physically changes at the end of the reaction
(iii) A catalyst takes part in the chemical reaction
(iv) A catalyst can induce chemical reaction
21. The catalyst used for the oxidation of ammonia to nitric acid is :
(i) Cupric chloride (ii) Iron oxide
(iii) Platinum (iv) Manganese dioxide
22. A substance that regards the rate of chemical reaction in the presence of a catalyst
is called :
(i) An inhibitor (ii) A positive catalyst
(iii) An autocatalyst (iv)A promoter
23. A catalyst poison is essentially:
(i) A homogeneous catalyst (ii) A heterogeneous catalyst
(iii) An inhibitor (iv) An autocatalyst
24. Catalyst poisons (temporary poisoning) act by :
(i) Chemically combining with the catalyst
(ii) Getting adsorbed on the active centres on the catalyst surface
(iii) Chemical combination with anyone of the reactants
(iv) Coagulating the catalyst
25. Which of the following types of the metal make the most effiCIent catalyst?
(i) Transition metals (ii) Alkali metals
(iii) Alkaline earth metals (iv) Coloured metals
26. Which one of the following statements is incorrect?
(i) Presence of a catalyst does not alter the equilibrium concentration in a
reversible reaction
(ii) Change of temperature alter the rate of catalysed reaction in the same
proportion as of the reaction without catalyst
(iii) Homogeneous catalysis depends upon the nature and extent of the surface
(iv) Change of a catalyst may change the nature of the reaction
27. Enzymes are:
(i) Microorganisms (ii) Proteins
(iii) Inorganic compounds (iv) Moulds
CHEMICAL KINETICS & CATALYSIS 273
15. In the conversion of urea into ammonium carbonate ................. acts as a catalyst.
16. 2502 + O2 ~ 2S0 3 is an example of .............. catalysis.
He!
17. CH 3COOCH 3 + H20~ CH 3COOH + C 2H50H is an example of .......... .
catalysis.
18. ~ 2NH , Mo acts as ............. .
In N2 + 3H2 ~ 3
19. A catalyst poison is essentially a ............... .
20. The presence of a catalyst ............ the activation energy of the reaction.
True or False
State whether the following statements are true (T) or
false (F)?
1. The value of temperature coefficient is nearly 10.
2. All radioactive emanations are of first order.
3. The inversion of cane sugar by HCI is of second order.
. ,, 4. The reaction rate is proportonal to the surface area of reactant.
15. A catalyst remains unchanged in mass and chemical composition at the end of
a reaction.
16. A large quantity of catalyst is required to bring about a reaction.
17. The substance which increases the activity of a catalyst is called an activator.
18. A promoter decreases the peaks and cracks on the catalyst surface.
19. Enzyme ptyalin present in h)lman saliva changes starch into glucose.
20. The presence of a catalyst increases the activation energy of the reaction.
21. In homogeneous catalysis, the intermediate compound is formed at lower acti
vation energy.
22. A catalyst cannot be recovered unchanged chemically at the end of the reaction.
ANSWERS
1. (a) ,2. (b) 3. (b) 4. (c) 5. (b) 6. (a) 7. (b) 8. (c) 9. (a) 10. (d) 11. (c) 12. (d)
llWK~~~~~nWm~~~·Wn~nWn~u~
25. (a) 26. (c) 27. (b) 28. (b) 29. (c) 30. (a) 31. (c) 32. (a) 33. (d) 34. (d) 35. (a) 36. (c)
37. (b) 38. (c) 39. (c) 40. (c) 41. (b) 42. (d) 43. (c) 44. (b) 45. (d) 46. (a) 47. (c) 48 (d)
49. (d)
True or False
1. (F), 2. (T), 3. (F), 4. en,
5. (T), 6. (F), 7. (F), 8. (T),
9. (T), 10. (F); 11. (F), 12. (T),
13. (T), 14. (F), 15. (T), 16. (F),
17. (T), 18. (F), 19. en, 20. (F),
21. (T), 22. (F)
DOD