Introduction to Thermodynamics 1

Chapter 1

Introduction to Thermodynamics
Introduction
The subject of thermodynamics deals basically with the interaction of one body with another in terms of the
quantities of heat and work. The entire formulation of thermodynamics is based on the two fundamental laws
which have been established on the basis of the experimental behaviour of macroscopic aggregates of matter
collected over a long period of time. With the help of thermodynamics principles the experimental criteria for
equilibrium or for the spontaneity of process are readily established
Mathematics Involved in Chemical Thermodynamics
Differential Formulas:
d (c ) d (xn )
(i) 0 (ii) = nxn–1
dx dx
d (cx n ) d ( xn ) d (sin x)
(iii) =c = cnx(n–1) (iv) = cos x
dx dx dx
d (cos x) d (a x )
(v) = – sin x (vi) = ax ln a
dx dx

d (e x ) d (ln x ) 1
(vii) = ex (vii) = , x>0
dx dx x
d [ f ( x) g ( x )] d [ g ( x )] d [ f ( x)]
(ix) = f(x) + g(x)
dx dx dx

d [ f ( x )] d [ g ( x)]
d  f ( x)  g ( x)  f ( x)
(x) = dx dx
dx  g ( x)  [ g ( x)]2

Integration Formulas:

n x n1
(i)  dx = x + c,  dt  t  c (ii)  x dx = c
n 1

n x n1
(iii)  kx n dx = k  x dx  k c x x
(n  1)
(iv)  e dx = e +c

1
(v)  x dx = n x + c
e (vi)  sin x dx = – cos x + c
2 Introduction to Thermodynamics

(vii)  cos dx = sin x + c

d 
(viii)  [ f ( x ) g ( x)] dx = f(x)  g ( x )dx -   f ( x ). g ( x )dx  dx
 dx 
Logarithms:
(i) log10 2 = 0.3010 (ii) log10 3 = 0.4771 (iii) log10 4 = 0.6020
(iv) log10 5 = 0.699 (v) log10 6 = 0.7781 (vi) log10 7 = 0.8451
(vii) log10 8 = 0.9030 (viii) log10 9 = 0.954 (ix) log10 10  1

Important Rules of Logarithms:

(i) ln 2  2.303  log10 2  2.303  0.3010  0.6932

m
(ii) log10 x m  m log10 x ; log  log m  log n
n
(iii) log( m  n)  log m  log n

2 1
(iv) log10 x  2  x  10   0.01
100
(v) log10 (a / b)  log 10 a – log 10 b

Important Conversion Factors

(i) 1 cal  4.184J  4.184  107 erg
(ii) Newton  105 atm cm3
(iii) Joule = 107 ergs = 0.239 cal
(iv) Electron Volt, 1 eV = 1.6021 ×1012 erg molecule –1
 1.6021 1019 J molecule 1
 96.48 kJ mol 1  23.06 kcal mol1
 8065.5 cm 1
(v) 1 atm = 760 mm Hg = 760 Torr = 101325 N M–2 = 101.325 kPa
(vi) 1 mm Hg = 1 torr = 133.322 N M–2
(vii) 1 a.m.u. = 1.66×10–24 g = 1.66 × 10–27 kg  931.5 MeV
(viii) 1 cm–1 = 1.986 × 10–23 J = 1.240 × 10–4 eV
(ix) 1 D = 3.336 ×10–30 cm
(x) 1 Å = 10–8 cm = 10–10 m
Introduction to Thermodynamics 3

Function?
Function is a rule that relates two or more variable.
If z  3x  y , where z is a function of x and y . In ideal gas equation P is a function of T and V , T is a function
of P and V and V is a function of T and P.
Operator:
An operator is a symbol for a rule for transforming a given mathematical function into another function. It has no
physical meaning if written along. It is represented by cap (^).

Example:
d
(i) is an operator which transforms a function into its first derivative with respect to x.
dx
d
(ii) transforms the function sin x into the function cos x .
dx
In general, if  denotes an operator which transforms the function f  x  into the function g  x  , then we

write Âf  x   g  x  .

Example:
d d
(a) Let  be and f  x   ax 2 ; then Âf  x    ax 2  2ax i.e. g  x   2ax .
dx dx
(b) Let  be a (i.e. multiplication by a ) and f  x   x 2  c , then Âf  x   a.  x 2  c   ax 2  ac i.e.

g  x   ax 2  ac .

Differentiation:
In calculus (a branch of mathematics) the derivative is a measure of how a function changes as its input
changes. Derivative can be thought of as how much one quantity is changing in response to changes in some
other quantity; for example, the derivative of the position of a vehicle with respect to time is the velocity at
which the vehicle is traveling. The process of finding a derivative is called differentiation. The reverse process
is called antidifferentiation. The fundamental theorem of calculus states that antidifferentiation is the same as
integration.
Differentiation is a method to compute the rate at which a dependent output y changes with respect to the
change in the independent input x. This rate of change is called the derivative of y with respect to x. The
dependence of y upon x means that y is a function of x. This functional relationship is often denoted y = ƒ(x),
where ƒ denotes the function. If infinitesimal change in x is denoted by dx, and the derivative of y with respect
dy
to x is written as .
dx
In mathematics, a partial derivative of a function of several variables is its derivative with respect to one of
those variables, with the others held constant as opposed to the total derivative.
For a function of several variables, for example f(x,y,z), the partial derivatives are simply usual derivative in
one of the variables when you keep the other variables fixed. For example, take
f  3xy  yz 2
In this example f is a function of x,y and z and we can calculate the value of partial derivative in all form
 f   f   f 
 x  ;  y  ;  z 
  y,z   x ,z   x,y
4 Introduction to Thermodynamics

Total derivative is just the usual derivative (with respect to x) of the function f. It can be expressed in terms of
partial differentiation as
 f   f   f 
df    dx    dy    dz
 x  y,z  y  x,z  z  x,y
Cyclic Rule :
The triple product rule, known variously as the cyclic chain rule, cyclic relation, or Euler’s chain rule, is
a formula which relates partial derivatives of three interdependent variables. The rule finds application in
thermodynamics.
x
The triple product rule for such interrelated variables x, y, and z
comes from using a reciprocity relation is given by
z y
 x   y   z 
       1
 y  z  z  x  x  y
This relation may be written in the form of Pressure P, Volume V and Temperature T.
Cycic Rule in the form of P, V & T:
Let us consider one function and any two variables then we proof that cyclic rule
P  f T , V 

 P   P  P
dP    dT    dV
 T V  V T
Since, P is constant, so dP = 0 T V

 P   P 
0  dT    dV
 T V  V T
 P   P 
Or,  T  dT    V  dV
 V  T
 P   T   P 
Or,  T   V     V 
 V  P  T
 P   T   V 
Or,        1
 T V  P V  T  P

Thermodynamic Coefficient:
(i) Isobaric thermal expansion coefficient   :
The degree of expansion divided by the change in temperature at constant pressure is called the material’s
coefficient of thermal expansion and generally varies with temperature
1  V 

V  T  P

(ii) Isothermal Compressibility factor    :

In thermodynamics and fluid mechanics, compressibility is a measure of the relative volume change of a fluid
or solid as a response to a pressure (or mean stress) change at constant temperature.
1  V 
 
V  P  T
Introduction to Thermodynamics 5
Note: most textbooks use the notation κ for this quantity.
where, V is volume and P is pressure
The above statement is incomplete, because for any object or system the magnitude of the compressibility
depends strongly on whether the process is adiabatic or isothermal. Accordingly isothermal compressibility is
defined:
1  V 
T   
V  P T
where the subscript T indicates that the partial differential is to be taken at constant temperature
Adiabatic compressibility is defined:
1  V 
s   
V  P s

(iii) Isochoric Thermal Pressure Expansion Coefficeint    :

The relative change in pressure with respect changing temperature at cosntant volume known as isochoric
thermal pressure expansion coefficient.
1  P 
  
P  T  V

State Function:
In thermodynamics, a state function, state quantity, or a function of state, is a property of a system that
depends only on the current state of the system, not on the way in which the system acquired that state. For
example, internal energy, enthalpy and entropy are state quantities .In contrast, mechanical work and heat are
process quantities .
To prove: State function we use Euler’s theorem. This theorem applies on linear equation (Not zig-zag
equation according to Euler)
If z is function of x and y variable.

z  z  x, y 

 z   z 
dz    dx    dy
 x  y  y  x
 z   z 
Put , M   , N  
 x  y  y  x
So, equation change from zig-zag to linear
dz  Mdx  Ndy
Than for z being a state function it must follow this relation.
System and Surroundings
A system is that part of universe which is under thermodynamic study and the rest of universe is called surroundings.
A system is made up of one or more than one phase and is called homogenous and heterogenous systems
respectively.
A phase is defined as homogenous, physically distinct and mechanically seperable portion of system.
Types of system:
Depending upon nature of boundary between system and surroundings:
(a) Isolated system: If the boundary prevents any interaction with the surroundings, the system is called
isolated system.
Or
 6 Introduction to Thermodynamics
A system is said to be isolated when it can neither exchange energy nor matter with its surroundings.
e.g. – Boiling water, A cup of tea in thermus flask.
(b) Open system: If the matter & energy both can pass across the boundary, the system is called open system.
e.g. – Tea kept in cup.
(c) Closed system: If matter can’t exchange but energy exchange it is called closed system.
e.g. – Tea kept in kettle.
Thermodynamic process:
It is the path or operation by which a system changes from one state to another.
1. Isothermal process: Temperature of system remains constant during each step.
T = constant.  dT  0
Details:
(i) For such change system should be contained in a perfectly coducting container.
(ii) Perfect isothermal change is impossible but when a change is carried out very slowly approximate isothermal
change occurs.
(iii) It follows Boyle’s law.
(iv) Work done in isothermal process is graphically given by area under P-V curve.
(v) H  nC P .T & E  nC V .T
In isothermal process T  0
 H  0 & E  0
(vi) Specific heat at constant T is infinitely great in isothermal process.
2. Adiabatic process: There is no heat exchange between system & surroundings.
q = constant.
dq = 0
Perfectly adiabatic change is impossible but when a process is carried out very rapidly fairly approximate
adiabatic change occurs.
3. Isobaric process: It is the process in which pressure of the system remains constant during each step.
P = constant
dP = 0
4. Polytropic process: In this process heat capacity of the body remains constant.
CP = constant and CV = constant
dCP = 0 & dCV = 0
5. Quasistatic process: The processs in which the deviation from thermodynamic equilibrium is infinitesimal and
all the states through which the system passes can be considered as equilibrium states.
6. Isochoric process: When these is no change in the volume of the system during various operations the change
is said to be isochoric.
V = constant.
dV = 0
The combustion of a substance in a bomb calorimeter is isochoric process.
7. Cyclic process: The process which brings back a system to its original state after a series of changes is called
a cyclic process.
As the E & H depends only on their state.
 E & H  constant
& dE  0 & dH  0
Reversible process: A thermodynamically reversible process is one in which all changes occuring in any part
of the process are exactly reversed when it is carried out in opposite direction.
Characteristics of reversible process:
1. It has to be carried out in infinitesimal amounts and hence require infinite time. Therefore changes in this process
are very slow.
Introduction to Thermodynamics 7
2. At all time, during the process, the driving force for the change is opposed by a restraining force infinitesimally
smaller than the driving force.
3. It can be reversed by infinitesimal increase in opposing force.
4. The work produced in a reversible process is maximum.
Irreversible process: The process which occurs suddenly or spontaneously without the restriction of occuring
in successive stages of infinitesimal quantities.
For such process driving force is very much greater than opposing force; so these can’t be reversed.
These are also called spontaneous process.

Characteristics of irreversible process:

1. If the changes be reversed, the work in the forward direction and in the backward process would be unequal.
2. If initial and final stages be specified, the internal energy change would always be same, whether the process
has been affected reversibly or irreversibly.
3. In an irreversible process, since work terms (dw) in two opposite directions are unequal, the heat transfers
(dq) would also be unequal.
4. All natural processes are irreversible.
e.g.  (i) flow of heat from high temperature to low temperature;
(ii) Exapansion of gas from higher pressure to lower pressure.
Internal Energy:
Inernal energy is the energy associated with a system by virtue of its molecular consitution and motion of its
molecules.
It depends upon internal potential energy and internal kinetic energy.
ETotal = Internal potential + Internal kinetic enegy
E Total  E t  E r  E v  E b  E e  E O  VT  E nuc
where Et = Translational K.E.
Er = Rotational K.E.
EV = Vibrational K.E.
Eb = Bond energy
Ee = Electronic energy
E0 = Zero point energy
Enuc = Energy due to interaction between nuclei.
VT = Intermolecular interaction energy.
 It is an extensive property ( E & E both).
 Internal energy is a state function.
dE  E 2  E1  Efinal  Einitial
It follows Euler’s theorem of Exactness.

Sign of E:
1. If E1  E 2  E   ve
i.e. energy will be absorbed by the sytem from its surroundings. Hence reaction will be exothermic.
 For cyclic process
 E  0 ;  dE 0 A Path 1


Path 2 B

V
 8 Introduction to Thermodynamics

Work:
Any quantity that flows across the boundary of a system during a change in its state and is completely convertible
into the lifting of a weight in the surroundings.
1. Pressure - Volume work/work of expansion of gas:
W    Fext  distance through which piston moves        Fext  Area     

W  Pext .V  Area    V 

Or W  Pext  V2  V1 

(a) for expansion V2  V1 , thus W = negative

(b) for compression V1  V2 , thus W = positive
2. Isothermal reversible expansion work of ideal gas
Pext

Pint Vi=V1 Vf =V2

Expansion will take place only when

Pint > Pext
Where, Pint= Pressure exrted by gas (Internal Pressure)
Pext= External pressure or atmospheric pressure
V2

Work done, W= – d W  –  Pd V
V1

V2

W= –  pd V (w = –pdV) ... (1)

V1

For an ideal gas, we know that

PV= nRT
nRT
P=
V
Putting this value of P in equation (1), we get
V2 nRT V2 dV V
 V2 
W= V1 V
dV ; W= – n RT V1 V
; W= – n RT [ln V]V12 = – n RT ln  
 V1 

 V2 
 W= – 2.303 nRT log10  
 V1 

V 
W= –2.303nRTlog10  2 
 V1 

Since V2 > V1 (due to expansion)

V2 V 
  1  log  2   1 ; W< 0
V1 10  V 
1

i.e Wisothemal < 0

i.e. Work is done by the system.
Introduction to Thermodynamics 9
Problem-1. If 2 mol of an ideal gas get expanded reversibly from 8dm3 to 24dm3. Then calculate the total
amount of heat in the isothermal process at 27°C.
Soln. We know that in case of reversible isothermal expansion of an ideal gas, the work done is given by-
 V2 
W= – 2.303 nRT log10   ... (1)
 V1 
Here n=2
T = 27°C = 27 + 273 = 300 K
J
R = gas constant = 8.314
K.mol
V1 = 8 dm3; V2 = 24 dm3
Putting all these values in equation (1), we get
 J  24dm3
W = – 2.303 × (2 mol) ×  8.314   log10 × 300 K
 K mol  8dm3
 W = – 2.303 × 2 × 8.314 × 300 log10 (3) J
 W = – 2.303 × 8.314 × 600 × 0.4771 J
 W = – 5481.0608 J
Now from the first law of thermodynamics we know that dQ = dU + dW
 dQ = nCV dT + dW
 T  constant 
 dQ = 0 + dW  dT=0 
 
 Q=W
 Total amount of heat = – 5481.0608 J
V P
Wrev   nRTn 2   nRT n 1
V1 P2
3. Isothermal irreversible expansion work of an ideal gas
(i) Free expansion (in vacuum):
When an ideal gas is expanded isothermally in vacuum from a volume V1 to V2 irreversibly, Then
Work done = – Pext (V2–V1) [ w = – PdV]
=0 [Since in vacuum there is no external pressure on the gas]
(ii) When the ideal gas is expanded isothermally from a volume V1 to V2 irreversible upto a constant external
pressure Pext and if Pext < Pgas, then
Work done = – Pext (V2 –V1 )
* Is an adiabatic process
* Sudden change in temperature takes place.
* Cooling occurs very rapidly.

4. Reversible adiabatic expansion of an ideal gas:

Starting with the proof of TV  1  constant
Proof : From the 1st law of thermodynamics, we know that,
dQ = dU + dW ... (1)
But for an adiabatic process, Q is constant i.e dQ = 0
(1) 0 = dU + dW
dU +dW= 0
dU + dW= 0
 nCV dT + PdV = 0 ... (2)
 10 Introduction to Thermodynamics

[dU = nCVdT & dW = PdV]

For one mol n = 1
 (2)  CV dT + PdV = 0
 CV dT + PdV = 0 ... (3)
Now for one mole of an ideal gas, we know that
RT
PV = RT; P =
V
Now putting this value of P in equation (3), we get
 RT  dT dV
CV dT +  V  dV= 0  CV R =0
T V
dT dV
 CV  (CP  CV ) =0 [ R = CP – CV]
T V

dT  CP  dV dT dV
  1 = 0      1 =0
T  C V  V T V

dT dV
Integrating both sides, we get      1  =0
T V
 1
 lnT + ( –1) ln V= ln C  ln T + ln V = lnC
 ln TV  1 = lnC
Taking antilog, we get TV  1 = C
i.e. TV   1)  constant ... (4)
Now, for 1 mol of an ideal gas, we know that,
PV= RT  T= PV
R
Putting this value of T in (4) , we get
 PV  (  –1)
 V = constant
R 

 PV   constant ... (5)

[ R is also a constant]
Again, for one mol of an ideal gas, we have
RT
PV = RT  V= P
Now putting this value of V in equation (4). we get
 1
 RT 
T = constant
 P 

T  P
1 
 constant

Problem-2. A given mass of a gas at 0ºC is compressed reversiblly and adiabatically to a pressure 20 times the
initial value calculate the final temp of the gas. (= 1.42)
Soln. We know that,

T P(1–) = Constant
 T1 P1(1– ) = T2 P2(1– )
 (1 )
 T1   P2 
  T  =  P  ... (1)
2 1
Introduction to Thermodynamics 11
Here,
T1 = 0°C = 273 K, T2 = ?, P1 = P1, P2 = 20P1 &  = 1.42
Putting all there values in Equation (1), we get
1.42 11.42 1.42
 273   20 P1   273 
 T  =  P    T  = (20)–0.4.2
2 1  2 

 273
Taking log, we get, 1.42 log10  T  = – 0.42 log10(20)
2

 1.42 log10 (273) – 1.42 log10 T2 = – 0.42 log10(2×10)

 1.42 log10 T2 = 1.42 log10 273 + 0.42 log10 2log10 10
 = 4.00577/1.42 = 2.820965
log10 T2
 Taking anti log = 102.820965 = 66.2.16 K
5. Work done in reversible adiabatic expansion for an ideal gas:
V2

 dw = –  V1
PdV ... (i)
V2
 w= –  V1
PdV ... (ii)

Now we know that for adiabatic process, PV   constant

 PV   K  P  KV
Also P1V1  P2 V2  K ... (iii)
Now putting this value of P in equation (ii), we get
V2
V2 V2  V –  +1 
w = – V KV dV ; w= –K V –
V dV  w= –K 
–

1 1    1 V1

K1– 1–
 w= 1    V2  V1 

1 1– 1–  1–  1
 1 
 w= (1  )  KV2  KV1  ; w= (  1)  P2 V2 V2  P1V1 V1  [Using (iii)]

1
 w (P2 V2  P1V1 ) ... (iv)
(  1)
Now for an ideal gas, we know that, PV = nRT
 P1V1= nRT1 ... (v)
& P2V2 = nRT2 ... (vi)
equation, (vi)–(v)
 P2V2 – P1V2 = nR(T2 – T1)
Now making this substitution in equation (iv), we get
1
w nR(T2  T1 )
(  1)

6. Work done in irreversible adiabatic expansion for an ideal gas:

(i) Free expansion (in vacuum):
When an ideal gas is expanded adiabatically (in vacuum) from a volume V1 to V2 irreversibly, Then
work done = – Pext (V2–V1)
=0
[Since in vacuum there is no external pressure on the gas]
 12 Introduction to Thermodynamics

(ii) When the ideal gas is expanded adiabatically from a volume V1 to V2 irreversibly upto a constant external
pressure Pext and if Pext < Pgas, Then
Work done= – Pext (V2–V1) ... (i)
Now from the 1st low of thermodynamics, we know that
dQ= dU + dW
0= dU + dW [ For adiabatic Process Q = constant]
 0= nCVdT + PdV; 0= nCV(T2 –T1) + P(V2 –V1)
nC V
 –P(V2 –V1)= nCV(T2 –T1); (V2 –V1)= – (T2 –T1)
P
Now making this substitution in equation (i), we get

 Work done= nCV Pext (T2 – T1) [Where, P is pressure of the gas]
P
Problem-3. Two moles of a monoatomic gas expand adiabatically in a reversible manner on heating 27°C to
327°C.Then calculate total change in internal energy of the entire process.
Soln: We know that, chnage in internal energy (dU) is given as
dU= nCVdT
 dU= nCV (T2 – T1) ... (i)
Here, dU= change in internal energy.
n= 2 moles
3  3

CV= R  For monoatomic gas CV  2 R 
2  
T1= 27°C = (27 + 273) K = 300 K
T2= 327°C = (327 + 273) K = 600 K
Now putting all these values in equation (i), we get change in internal energy
3 cal
 dU= 2mol×  R(600 – 300) K = 3 × 2 ×  300 mol K
2 k.mol
 dU= 1800 cal
Second Method: We know that, work done in reversible adiabatic expansion (w) is given as:
nR n (C P  C V )
l  nR (T2  T1 ) (T2  T1 )
    nC V R
w= (T2 – T1) =  C P  1 =  CP – CV  = (T2 – T1) = nCVdT
( –1) R
 CV   CV 
= dU (Change in internal energy)
So, dU  nCV dT
i.e. in reversible adiabatic expansion, the work done is equal to the change in internal energy.