THERMODYNAMIC EQUILIBRIUM 1.

Mechanical Equilibrium

2.Thermal Equilibrium
3.Chemical Equilibrium QUASISTATIC PROCESS In which the deviation from thermodynamic

equilibrium is infinitesimal and all the states through

which the system passes during a quasistatic process can be considered as equilibrium states.
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internal energy : the energy content of a system. 1. kinetic energy of molecules (due to vibrational,

Internal Energy and Temperature

rotational or electronic energy)

2. Potential energy due to intermolecular forces , depends upon separation .

3. the energy of electrons and nuclei The relationship between energy and monatomic ideal gas) 1 3

temperature

(for

av KE/molecule =

m v2

k BT

Internal Energy U = number of molecules av KE/molecule = N (3/2) kBT = (3/2) n RT = (3/2) P V (ideal gas) Internal energy can change by thermodynamic process

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====== ZEROth LAW of Thermodynamics =====

If two systems A and B are separately in thermal equilibrium with a third system C, then A and B are in thermal equilibrium with each other.

Work : A path dependent function

The work done is the area under the curve in a PV diagram. The work done depends on the path by which the system goes from the initial to the final state. The work done depends on the initial, final and intermediate states of the system.
What is the total work done by system when going from state 1 to state 2 to state 3 and back to state 1 ?
P P1 P3
1 2

Area = (V2-V1)x(P1-P3)/2
3

V1

V2

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Isobaric Process: P=constant Isochoric Process: V=constant

Wtot = ??

P
1

W = PV (>0)
2

P
1

W = P V = 0
2

P
4 3 4 3

Wtot > 0
4 3

V > 0

V = 0 V

P
1

W = PV (<0)
2

P
1

W = P V = 0
2

V
P
1

If we go the other way then 3 Wtot < 0 V

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V < 0

V = 0 V

Work done during volume change Work can be performed by gas system by changing
volume dW=Fdx=PAdx at constant pressure P and Area A
A

W P dV
V 1

V2

Work done is the area under the P-V curve.

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The First Law of The amount of Thermodynamics heat supplied to the system is equal to the sum
of the increase in the internal energy (U) of the system and the external work done (W) by the system.

Q=(U2-U1)+W
For a very small change in the state of the system

Q=dU+W

or

dU = Q - PdV

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Significance of the first law

It is applicable to any process by which a system
undergoes a physical or chemical change

It introduces the concept of internal energy, and

It provides method for determining the change in

internal energy

Limitations of the first law

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Path between thermodynamic states

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Path between thermodynamic states

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First Law of Thermodynamics Example-1

2 moles of monatomic ideal gas is taken P from state 1 to state 2 at constant pressure P=1000 Pa, where V1 =2m3 and V2 =3m3. Find T1, T2, dU, W, Q.
P
1 2

1. P V1 = n R T1 T1 = P V1/(nR) = 120K

V1

V2

2. P V2 = n RT2 T2 = P V2/(nR) = 180K

3. U = (3/2) n R T = 1500 J or U = (3/2) P V = 1500 J

4. W = P V = 1000 J > 0 Work done by the system (gas)

Q = U + W = 1500 J + 1000 J = 2500 J > 0 heat gained by system (gas) 24

First Law of Thermodynamics Example-2

2 moles of monatomic ideal gas is taken from state 1 to state 2 at constant volume P V=2m3, where T1=120K and T2 =180K. P2 2 Find Q. 1. P V1 = n R T1 P1 = n R T1/V = 1000 Pascal
P1
1

2. P V2 = n R T1

P2 = n R T2/V = 1500 Pa

3. U = (3/2) n R T = 1500 J
4. W = P V = 0 J

5. Q = U + W = 0 + 1500 = 1500 J 25 => It requires less heat to raise T at const. volume than at const. pressure.

Thermodynamic Processes
Isothermic: constant temperature T = 0 means U = 0 (U is constant!) Adiabatic: no gain/loss of heat energy (Q) Q = 0 means U = W Note: Isothermal and Adiabatic are important for Carnot Engine (Ideal heat Engine) Isochoric (or isovolumetric): constant volume V = 0 means W = 0 (no work performed on/by system) Isobaric: constant pressure P = 0 means W = PV
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(for gases)

Note: Isochoric and Isobaric are important for specific heat of

 The heat (Q) absorbed by a gas can be expressed as:

Specific Heat Capacity & 1st Law of Thermodynamics (for monatomic gases)

Q = CnT
where C is the molar heat capacity (J/mol.K) For gases it is necessary to distinguish between molar heat capacity at 27 constant pressure (CP) and constant

Lets begin with the 1st Law of Thermodynamics:

Q = U + W
At constant pressure: {U = (3/2)nRT & W = PV = nRT}

Specific Heat Capacity & 1st Law of Thermodynamics (for monatomic gases)

Q = (3/2)nRT + nRT = (5/2)nRT CP = (5/2)R At constant volume: {U = (3/2)nRT & W = 0} Q = (3/2)nRT + 0 = (3/2)nRT CV = (3/2)R
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P-V relation for Adiabatic Processes

When a gas undergoes an adiabatic expansion/contraction the relationship between pressure and volume is PiVi = PfVf where is CP/CV
For monoatomic gases, is 5/3
For Diatomic gases, is 7/5
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Selected Specific Heats

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An ideal gas is taken through a cycle abc consisting of the following processess:

ab, isothermal expansion at temperature T1 from volume V1 tp

2V1, bc, compression at constant pressure P1 to volume V1, and ca, change of pressure at constant volume. Find the expressions for the work done, the heat transferred and the change in the internal energy for each part of the cycle, and show that the sum of the three is zero for the internal energy only. P a

P1

b
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Study material on Thermodynamics

Book: Basic Thermodynamics - Evelyn Guha (Cahpter-3,4 & 5)
Worked Examples on first Law: Page-58,59,60 &61 (chapter-3)

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