CALORIMETRY

Total number of questions in this chapter are :

(i) In chapter Examples ....................... 06

(ii) Solved Examples ....................... 04

Total no. of questions ....................... 10

 Calorimetry is that branch of heat which deals with
fRT E
its measurement. the useual units of heat are calorie  E= and Cv =
2 T
or kilocalorie
Rf
1. SPECIFIC HEAT  CV =
2
This is also called ' Heat Inertia' of a substance (8) Amount of heat needed to increase the
1.1 Specific Heat of solid & Liquid (s) : If a solid or a temperature of n moles of gas by dT at constant
liquid is heated till the change of the state, there is volume is
no change in their volume hence the work done is d = ncv dT.
zero. Hence there is only one specific heat of solids (9) Amount of heat needed to increase the
and liquids which is constant. temperature of 1gm of gas by 10C at constant
1. Definition : The amount of heat needed for an volume is called gram specific heat at constant
unit increase in the temperature of unit mass of volume.
a solid or liquid is called it's specific heat
(C v ) molar
Unit : kilocalorie / kg-ºC or calorie/g-ºC (10) (Cv)gram =
M
1 Kcal / Kg-ºC = 1 Cal/g-ºC
or (Cv)molar = M(Cv)gram
2. If mass of the body is 'm' and specific heat is 's'
then amount of heat needed to increases it's where M = molecules wt . of gas
temperature by dT is given by Q = msdT (11) Amount of heat needed to increases temperature
3. Specific heat of water = 1 kcal / kg-ºC = 1 of 'm' gm of gas by dT at constant volume is
Cal/ g-ºC = 4.18 × 103 J/kg-ºC m
4. Kelvin can also be used instead of ºC is size of dQ = m (Cv)gram dT = (C ) dT
M v molar
both uints is same.
(12) Amount of heat needed to increase temperature
1.2 Specific heat of gas (C) of 1mole of gas by 10 C at constant pressure is
(1) There are many processes possible to give heat called molar specific heat at constant pressure.
to a gas. A specific heat can be associated to (13) Cp = Cv + R, for one mole.
each such process which depends on the nature where R = universal gas constant
of process. (14) Amount of heat needed to increase temperature
(2) The number of possible specific heats for a gas of n moles of gas by dT is at constant pressure
is infinite and the value of specific heats can dQ = nCp dT
very from zero (0) to infinity ().
Note : If gas is heated at constant pressure, then Cv can
(3) Generally two types of specific heat are
be replaced by Cp in above discussion. Hence
mentioned for a gas -
CP
(a) specific heat at constant volume (Cv) (a) (Cp)gram =
M
(b) specific heat at constant pressure (Cp) or Cp = M (Cp)gram
(4) These specific heats can be molar or gram, (15) Specific heat for other processes
depending on the amount of gas considered to  Q 
define it S  
 mT 
(5) The molar heat capacities of a gas are defined as (a) adiabatic s = 0, as Q = 0 but T has some
the heat given per mole of the gas per unit rise value
in the temperature
(b) isothermal s =  , as T = 0 but Q has some
(6) The molar heat capacity at constant volume, value
 Q  (16) Specific heat for any process is given by
denoted by Cv is Cv =  
 nT 
pdV pdV
(7) If, at absolute temperature T , total energy of a C = Cv + = Cp – R +
ndT ndT
gas E , degree of freedom of gas = f
(for the n mole of gas)
 Example : 4. LATENT HEAT
(1) If process is isochoric , then dV = 0
Latent heat of fusion of a substance is the quantity
 C = Cv of heat (in kilocalories) required to change its 1 kg
(2) If process is isobaric , then pV = nRT mass from solid to liquid state at its melting point
(For ice latent heat of fusion = 80 kilocal/kg).
pdV Latent heat of vaporization of a substnce is the
 = nR
dT quantity of heat required to change its 1 kg mass
from liquid to vapour state at its boiling point.
 C = Cv + R = C p (for one mole)
For water latent heat of vaporisation = 536 kilocal/kg
2 THERMAL CAPACITY
Specific heat, thermal capacity &
(1) Amount of heat needed to increase the latent heat
temperature of a substance (any amount) by 1ºC
Ex.1 The amount of heat necessary to raise the
is called thermal capacity of that substance.
temperature of 0.2 mol of N2 at constant pressure
(2) Thermal capacity = ( mass of body ) x (specific from 37º to 337º C will be -
heat)  Hc = ms (A) 1764 Joule (B) 764 Joule
(3) Unit = calorie /ºCor Kcal/ºC (C) 1764 Calorie (D) 1764 erg
Sol.[A] dQ = nCPdT
1
Heat capacity at point 'p' = = cot dQ = 0.2 × 7 × 300
tan 
dQ = 420 Calorie
(4) Thermal capacity is given by reciprocal of slope  dW = 420 × 4.2
of heat temperature curve.as dW = 1764 Joule
Q Ex.2 (Cp – Cv) will be -
Hc = mS = (A) Maximum for oxygen
dT
(B) Maximum for nitrogen
(5) Heat capacity in an isothermal process is infinite
(C) Maximum for carbon di oxide
(). e.g. process of melting and vaporisation
(D) Same for all gases
(6) If heat capacity of a body is Hc, then heat needed Sol.[D] (Cp – Cv) = R, where R is gas constant which is
to rise it's temperature by d is, dQ = Hc d same for all gases. So (Cp – Cv) is same for all
gases.
3. WATER EQUIVALENT OF A BODY
Ex.3 The ratio of radii of two copper spheres is
(1) If m gram of a substance is given Q amount of 2 : 1 and they are kept at same temperature. The
heat which rises its temperature by T . Now if ratio of their heat capacities will be -
on giving same amount of heat temperature of w (A) 2 : 1 (B) 1 : 1
gram of water is also increased by T then w is (C) 8 : 1 (D) 4 : 1
called water equivalent of body of mass m.
4
(2) The value of water equivalent of a body is same dQ 1  r13  S F
r1
G IJ FI
3
2
3 8
HK G HJK
3
as it's heat capacity. The difference is only in Sol.[C] dQ = = = =
4 r2 1 1
units. e.g If heat capacity of a body is m calorie/
2
 r2 3  S
3
0C then it's water equivalent will be m gram.
Ex.4 5 g of ice at 0°C is dropped ina beaker containing
20 g of water at 40°C, then
(3) Physical meaning : The same amount of heat (A) All the ice will not melt into water
has to be given to a body for increasing (B) All the ice will melt and the resulting
it'stemperature by dT as needed for quantity of temperature of water will be 0°C
water equal to it's water equivalent by same (C) All the ice will melt and the resulting
temperature range. temperature of water will be 25°C
(D) All the ice will melt and the resulting
temperature of water will be 16°C
Sol.[D] Heat required to melt 5 g ice = 5 × 80 = 400 cal. Heat (viii) If n1 moles of first gas at a temperarure T1 are
available with 20 g water at 40°C = 20 × 1× 40 mixed with n 2 moles of the other gas at a
= 800 cal out of this, 400 cal heat will be used to temperature T2 , the temperature of the mixture
melt the ice and remaining heat will raise the will be
temperature. Thus Heat given by water = Heat
taken by ice n1T1  n 2 T2
T= n1  n 2
20 × 1 × (40 –  ) = 5 × 80 + 5 × 1 × (  – 0)
800 – 20  = 400 + 5  Gaseous mixture
 25  = 400
Ex.5 n 1 and n 2 moles of two ideal gases of the
400 thermodynamics constants 1 and 2 respectively
or  = 25 =16°C
CP
are mixed C for the mixture is -
5. GASEOUS MIXTURE v

1   2
(i) Suppose two non - reactive gases are enclosed (A)
2
in a vessel of volume V. In the mixture n 1 moles
of one gas are mixed with n 2 moles of another n1  1  n 2  2
(B) n1  n 2
gas. If NA is Avogadro's number then number of
molecules of first gas will be N1 = n 1 NA and n1  2  n 2  1
number of molecules of second gas will be (C) n1  n 2
N2 = n2A2.
n1  1 (  2  1)  n 2  2 (  1  1)
(ii) Total mole fraction n = (n 1 + n 2). (D) n1 (  2  1)  n 2 (  1  1)
(iii) If M1 is molecular weight of first gas and M2
that of second gas the molecular weight of the Sol.[D] At constant temperature U = U1 + U2
mixture will be nCv = n 1 Cv1 + n 2 Cv2
Total number of mols. in the mixture
n1M1  n2 M2
M= n = n1 + n 2
n1  n2
R R
(iv) Specific heat of the mixture at constant volume nCv = n 1 + n2
1 1  2 1
will be
 CP =  C v
n 1C v 1  n 2 c v 2 R R
Cv =  nCP = n1 1 + n2 2
n1  n 2 1 1  2 1
(v) Specific heat of the mixture at constant pressure R R
will be n1  1  n2  2
CP 1 1  2 1
  = C = R R
n 1C p  n 2 c p 2 v
n1  n1
1
Cp = 1 1  2 1
n1  n 2

(vi) Ratio of specific heats of the mixture will be n1  1 (  2  1)  n 2  2 (  1  1)

=
n1 (  2  1)  n 2 (  1  1)
Cp n 1C p1  n 2 C p 2
= =
Cv n 1C v1  n 2 C v 2
Ex.6 One mole of monatomic gas ( = 5/3) is mixed
(vii) Pressure exerted by the mixture with one mole of a diatomic gas ( = 7/3), the
value of  for the mixture is
RT
P = (n1 + n2 ) (A) 1.40 (B) 1.50
V
Fm  m I RT (C) 1.53 (D) 3.07
= G
HM M JKV
1

1
2

2 7 5
n1C P1  n 2 C P2 1x 1x
(where m1 and m 2 are the masses of the two 2 2
Sol.[C]  = n C  n C = = 1.5
gases respectively) 1 V1 2 V2 5 3
1x 1x
2 2
 SOLVED EXAMPLE
Ex.1 1 g of steam at 100°C can melt how much ice at Ex. 3 5 g of ice at 0°C is dropped in a beaker containing
0°C? Latent heat of ice = 80 cal/g and latent heat 20 g of water at 40°C. What will be the final
of steam = 540 cal/g. temperature?
Sol. Heat required by ice for melting of m g of ice = Sol. Let final temperatue be = 
mL = m × 80 cal
Heat taken by ice = m1L + m1 c1   1
Heat available with steam for being condensed
and then brought to 0°C = 5 × 80 + 5 × 1 (  – 0)
= 1 × 540 × 100 = 400 + 5 
= 640 cal Heat given by water at 40°C
m × 80 = 640 = m2c2   2 = 20 × 1 × (40 –  )
640 = 800 – 20 
or m=  8 grams
80 As Heat given = Heat taken
Ex. 2 A tap supplies water at 10°C and another tap at 800 – 20  = 400 + 5 
100°C. How much hot water must be taken so
20  = 400
that we get 20 kg of water at 35°C ?
Sol. Let mass of hot water = m kg 400
 = = 16° C
mass of cold water 25
= (20 – m) kg Ex. 4 5 g ice of 0°C is mixed with 5 g of steam at 100°C.
Heat taken by cold water What is the final temperature?
= (20 – m) × 1 × (35 – 10) Sol. Heat required by ice to raise its temperature to
Heat given by hot water 100°C,
= m × 1 × (100 –35) Q1 = m1L1 + m1c1   1
Law of mixture gives = 5 × 80 + 5 × 1 × 100
Heat given by hot water = 400 + 500 = 900 cal
= Heat taken by cold water Heat given by steam when condensed,
m × 1 × (100 – 35) = (20 – m) × (35 – 10) Q2 = m2L2
65 m = (20 – m) × 25 = 5 × 536 = 2680 cal
65 m = 500 – 25 m As Q2 > Q1. This means that whole steam is not
or 90 m = 500 even condensed.
Hense temperature of mixture will remain at 100°C
500
m= = 5.56 kg
90