Concept of Work

Work is done when a Force ‘F’ moves through a distance ‘l ’

W = F .l
If Pext is not constant, then we have to look at
infinitesimal changes
δ W = F . dx
xf
where δ is inexact differential
W = ∫ δW = ∫ F dx hf
xi

Work is motion against an opposing force.

∫ mg dh = W
hi
grav

There are several types of work; gravitational, q ∫ E.dr = Welect

electrical, magnetic, surface, chemical Work
(work done on a charged particle by
(battery)
an electric field)

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 1

 Expansion / Compression Work

2 2
W = ∫ Pext Adx = ∫ Pext dV
1 1

Convention:
If a system is doing work on the surrounding, it is losing energy and regarded as –
ve by convention.
2
W = − ∫ Pext dV
Having a –ve sign implies W >0 if ∆V <0 , that is,
positive work means that the surroundings do
1 work to the system.
Integral depends on the path If the system does work on the surroundings (∆V
>0) then W <0.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 2

 Path dependence of work

V2 V2

W(1) = − ∫ Pext dV + 0 = − P1 ∫ dV = − P1 (V2 − V1 ) = P1 (V1 − V2 )

V1 V1

 V2  V2

W( 2) = 0 +  − ∫ Pext dV  = − P2 ∫ dV = − P2 (V2 − V1 ) = P2 (V1 − V2 )

 V1  V1
So work is not a function
Since P2 > P1 and V1 > V2 of state, it has path
dependence. It is wrong to
Hence W(1) < W 2 and ∫ δ W ≠0 write W(P,V)
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 3
 Heat Energy and Work Equivalence

Heat is a form of energy which transfers across the boundary of the system &
surrounding by virtue of the temperature difference.

Sign Convention : If heat enters into the system it is positive.

Equivalence of Work & Heat (Joule 1840)
It is possible to raise the temperature T1 → T2 such that T2 > T1

(1) With only heat

Heat like ‘W’ is a function of path. Heat is the energy
transfer that makes
use of the random
(2) With only work motion of atoms.

(3) With chemical reaction.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 4

 First Law of Thermodynamics

Law of Conservation of energy

“Total quantity of energy is constant, when energy disappears in one form, it
appears simultaneously in other form “

∆ ( Energy of System ) + ∆ ( Energy of Surrounding ) = 0

“When a system undergoes a transformation of state, the algebraic sum of different
energy changes, (heat exchanged, work done etc.) is independent of the manner of
the transformation. It depends only on the initial & final states of the
transformation.”

∫ dE = 0 For Closed system

The change of energy E during a transformation from normal

or reference state O to the state X is independent of the
manner of transformation. (The state of this system is defined
by its volume V and T temperature T)

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 5

 First Law of Thermodynamics

“During an interaction between system & its surrounding , the amount of energy
gained by the system must be exactly equal to the amount of energy lost by the
surrounding.”

For closed system energy interaction can be made via heat & work
dU = δ q + δ W

∫ (δ q + δ W ) = 0 The sum is a state function independent of path.

∫ δ q = − ∫ δ W Equivalence of heat & work.

∆ U sys = q + W ∆ U surrounding = − q − w SYSTEM

∆ U univers = ∆ U sys + ∆ U surrounding

SURROUNDING
∆ U universe = 0

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 6

 First Law of Thermodynamics

Clausius Statement of 1st Law:.

The energy of the universe is Conserved.

Cyclic device can operate because work done is a path function.

Wnet = W12 − W21 P

∫ dU = o Wnet

∫ q + W = o
⇒ q = −W V1 V2 V

Engine can only run in a cycle in order to convert heat into useful work.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 7

 Problem-Specific Heat Capacity

Problem: Calculate the amount of heat necessary to isobarrically raise the

temperature of one mole of CO2 (g) from 500 K to 2000 K, at P= 0.I MPa.
[Ans=8.188 104 J/mol]
Solution:

2000

q = ∫ C p dT q= ∫
500
(44.14 + 9.04 × 10 −3T − 8.54 × 10 5 T −2 ) dT

J
q = 81879
mol
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 8
 HW Problem-Work

Problem: Compare the work obtained from the two isothermal expansions
at 300 K of one mole of ideal gas following the paths shown in Figure 2.6.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 9

 Graphical representation of total derivative
A = xy
dA = dAx + dAy + dxdy
A′ = ( x + dx )( y + dy )
= xy + xdy + ydx + dxdy
dA = A′ − A
= xy + xdy + ydx + dxdy − xy
dA = xdy + ydx + dxdy
dA = dAy + dAx + dxdy
 ∂A   ∂A 
dA =   dy +   dx + dxdy
 ∂y  x  ∂x  y
dx → o dy → o dxdy → o
 ∂A   ∂A 
dA =   dy +   dx
 ∂y  x  ∂x  y

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 10

 Enthalpy

First law for Closed system

q + W = ∆U
q − PdV = U 2 − U1
At Const P
q p − P (V2 − V1 ) = U 2 − U1
q p = (U 2 + PV2 ) − (U1 + PV1 )
q p = H 2 − H1 = ∆H
∴ H = U + PV

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 11

 Specific Heat Capacity

First law of thermodynamics leads to useful relations:

U = U (V , T )
dU = δ q + δ W
 ∂U   ∂U 
dU = δ q − PdV dU =   dT +   dV
 ∂ T V  ∂V T
By Comparing
 ∂U    ∂U  
δq =  dT +  P +    dV
 ∂ T V   ∂V T 
At constant Pressure
At constant Volume Condition
 ∂q   ∂U    ∂U    ∂V 
 ∂q   ∂U  CP ≡   =  + P +    
CV ≡   =    ∂T  P  ∂T V   ∂V T   ∂T  P
 ∂ T V  ∂ T V
If system is heated at constant
If system is heated at constant volume pressure the change in energy of the
since no work is done therefore the system has additional component to
change in energy of the system is compensate expansion of volume.
entirely due to heat supplied.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 12

 Specific Heat Capacity

Take the difference of Cp and Cv

  ∂U    ∂V 
CP − CV =  P +    
  ∂V T   ∂T P

For an ideal gas PV = nRT For and ideal gas Internal energy is a
function of Temperature only.
For one mole of a gas PV = RT
 ∂U 
 ∂V    =0
P  =R  ∂V T
 ∂T  P
Hence

CP − CV = R

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 13

 Thermodynamic Cycle and Thermodynamic Properties

δq
Evaluate ∆U , ∆H , q, W , ∫T for a Cycle consist of A, B, and C processes.
Path ‘A’- Constant T 1 g ( p1,V1, T1 ) = 1 g ( p2,V2 , T1 )

∆U A = 0 dU = CV dT
∆H A = 0 dH = C p dT
nRT1
δ W = − pdV for Ideal gas p =
V
RT1
δW = − dV
V
V2
dV
W = − RT1 ∫
V
= − RT1 ln V V2
V1
V 1

V2
W = − RT1 ln
V1
CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 14
 Thermodynamic cycle and Thermodynamic Properties

Path ‘A’- Constant T (cont’d)

δ q + δ W = dU [ First Law of Thermodynamics]

q + W = ∆U ⇔ q = −W
V2
q A = −WA = RT1 ln
V1
δ q A = −δ WA
RT1
V2 2 dV 2
δ qA V dV V
∫
V1
T1
=∫
1
T1
= ∫R
1
V
= R ln 2
V1

“A process is reversible when its direction can be reversed at any point by an infinitesimal change
in external conditions”. Or System has no tendeney to change.

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 15

 Thermodynamic Cycle and Thermodynamic Properties

Path ‘B’- Reversible adiabatic 1 g ( p1,V1, T1 ) = 1 g ( p2,V2 , T2 )

qB = 0 ( Adiabatic)

dU = Cv dT dH = C p dT
∆u B = Cv (T2 − T1 ) ∆H B = C p (T2 − T1 )
q + W = ∆U
W = ∆U
∴WB = Cv (T2 − T1 )
δ qB
∫ T
=0 or dS = 0

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 16

 Thermodynamic Cycle and Thermodynamic Properties

Path ‘C’- Isochoric 1 g ( p3,V2, T2 ) = 1 g ( p2,V2 , T1 )

WC = 0 (Constant Volume)
∆U C = CV (T1 − T2 )
∆H c = C p (T1 − T2 )
q + W = ∆U ⇔ qC = CV (T1 − T2 )
δ q + δ W = dU
T1 T T
δ qC dU 1 CV dT 1
dT
∫ T
=∫
T2
T
=∫
T2
T
= CV ∫
T2
T
δ qC T1
∫
T
= CV ln T T1 = CV ln
T 2
T2

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 17

 Thermodynamic Cycle and Thermodynamic Properties
Comparison

[ A] Vs [ B] + [C ]

∆U A = 0 CV (T2 − T1 ) + CV (T1 − T2 ) = 0
∆H A = 0 C p (T2 − T1 ) + C p (T1 − T2 ) = 0
For adiabatic reversible
V2
q A = RT1 ln 0 + CV (T1 − T2 ) ≠ q A path for ideal gas
V1 γ −1
R
T1  V2  V  CV

V2 =  = 2 
WA = − RT1 ln CV (T2 − T1 ) + 0 ≠ WA T2  V1   V1 
V1 R
T1 V  CV

δ qA V2 T1 V2 ln = ln  2 
∫ T
= R ln
V1
0 + CV ln
T2
= R ln
V1
T2  V1 
T1 R V 
ln = ln  2 
T2 CV  V1 
δ qrev is a state function.
The result suggests that
∫ T

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 18

 Thermodynamic Cycle and Thermodynamic Properties

δq
Evaluate ∆U , ∆H , q, W , ∫T for a Cycle consist of A, D, and E processes.

Home Work
Problem

CH-501 Chemical Thermodynamics-III by Dr.-Ing. S. Mushahid (Lec 2-First Law of Thermodynamics) 19