UNIT 6: Thermodynamics - Part 2

Spontaneous and non-spontaneous changes A gas expands to fill the available volume. A hot body cools to the temperature of itts surroundings. A chemical reaction runs tn one direction rather than another. We can confine gas into a smaller volume. We can cool an object with a refregerator. We can force some reactions to go in reverse. None of these processes happen spontaneously, each must be brought about by doing work. The recognition of two classes of processes spontaneous and non-spontaneous, is summerized by the Second Law of Thermodynamincs. This law may be expressed as follows: No process is possible in which the sole result is the absorption of heat from a reservoir and its complete conversion into work.

6.1

Entropy

What determine the dirrection of spontaneous change? When a change occurs, the total energy of an isolated system remains constant but it is parcelled out in different ways. Spontaneous changes always accompnied by a dispersal of energy into a more disordered form. The Second Law of Thermodynamincs may be expressed in terms of another state function, the entropy, S. The entropy of an isolated system increases in the course of a spontaneous change. Stot > O 6.1

where Stot is the total entropy of the system and its surroundings. The thermodynamic definition of entropy concentrates on the change in entropy dS that occurs as a result af a physical or chemical change.

dS =

dq rev T

6.2

For a measurable change between two states i and f ,

S = if

dqrev T

Eqn 6.2 cabn be used to formulate an expression for the change in entrpy of the surroundings, Ssur

dS sek =

dq sek, rev T

where dq sur is an infinitesimal transfer of heat to the surroundings. For a measurable change

S sek =
For adiabatic change, qsek = 0, so

q sek T sek

6.3

Ssur = 0. The integral of eqn 6.2 around an arbitrary cycle is zero. The the entropy is the same at the initial and final states regardless the path taken between them.

6.2 Carnot cycle

dqrev =0 T

V Reversible isothermal expansion from A B at Th. The entropy change is dS = q h/T h (q h is the heat supplied to the system at high temperature, T h) Reversible adibatic expansion from B C. The entropy change is zero since no heat leaves the system. The temperature falls from Th to Tc Reversible isothermal expansion from C D at Tc . The entropy change is dS = - qc /Tc (qc is the heat released from the system) Reversible adibatic compression from D A. The entropy change is zero since no heat enters the system. The temperature rises from T c to Th. The total entropy around the cycle

1.

2.

3.

4.

dS = Th + Tc
qh qc = Th Tc

qh

qc

=0

The Clausius inequality Consider the system in thermal and mechanical contact with its surroundings at the same temperature, T. The system and the surroundings are not necessary in eqilibrium. Any change of state is accompanied by a change in entropy of the system, dS, and of the surroundings, dSsur. The process might be irrevisible, the total entropy will increase. dSsis + dSsek 0 or dSsis -dSsek dSsek = -dq/T dq is the heat supplied to the system. dqsek = -dq dS dq/T This expression is the Clausius ineqality. For isolated system, dq = 0, the Clausius inequality dS 0 For irrevisible adiabatic system, dq = 0 dS 0 6.6 6.5

6.4

6.3 Expansion of perfect gas

Consider the perfect gas expands isothermally and irreversibly From the first law dq = -dw since dU = 0. If the gas expand freely into a vacuum, it does no work. dw = 0 dq = 0 According to the Clausius inequality dS 0

Next, consider the surroundings. No heat is transferred into the surroundings. dSsek = 0 The total entropy change dStot 0 The change in entropy for a perfect gas that expands isothermally from Vi to Vf is S = nRln (Vf /Vi) 6.7

6.4

The entropy of phase transition

When a substance vaporizes, a compact condensed phase change into a widely dispersed gas, the entropy of the substance increases. The entropy oa a solid increases when it melts into liquid. At the transition temperature, any transfer of heat between the system and its surroundings is reversible because the two phases in the system are in equilibrium. q = Htrs Strs = Htrs /Ttrs

At constant pressure,

The change of molar entropy,

6.8

Trouton's rule A wide range of liquids give approximately the same standard molar entrpy, about 85 JK -1 mol-1. The standard molar enthalpy of liquid can be predicted by using Trouton's rule. Hvap o = Tb x (85 JK-1 mol-1)

6.9

6.5

The variation of entropy with temperature

The entropy of a system at a temperature Tf from a knowledge of its entropy at temoerature Ti and the supplied to change its temperature

S(T f ) = S (Ti ) + if

dqrev T

dq rev = CpdT At constant pressure

S (T f ) = S (Ti ) +
At constant volume, Cp replaced by Cv.

CpdT T

6.10

dT i T = S (Ti ) + Cp ln( Tf / Ti ) S ( T f ) = S ( Ti ) + Cp

6.6

Entropy measurement

The entropy of a system at a temperature T is related to its entrpy at T = 0. By measuring its heat capacity Cp at the different temperatures and evaluating integral in eqn. 6.10.

S(T ) = S(o) +

Tf

H T Cp g) Cp( p)dT Tb Cp(c) ( + dT + vap + dT 6.11 Tf Tb T T Tb T

The third law of thermodynamic At temperature T = 0, all energy of thermal motion has been quenched, and in a perfect crystal all the atoms or ions are in regular uniform array. The absence of both spatial disorder and thermal motion suggests that the materials have zero entropy. According to Nernst heat theorem: The entropy change accompanying physical and chemical

trannsformation approaches zero as the temperature approaches zero. Hence, all perfect crystals have zero entropy at T = 0

The third law of thermodynamics can be expressed as

If entropy of every elemment in its most stable state at T = 0 is taken as zero, then every substance has a positive entropy which at T = 0 may become zero, and which does become zero for all perfect crystalline substances, including compounds.

Standard reaction entropy, S r o The Standard reaction entropy, Sr o is defined as the difference between the molar entropies of the pure, separated products and the pure, separated reactants, all substances being in their standard states at the spesified temperature. Sr o = Sm o - Smo products reactants 6.10

6.7

The Helmholtz and Gibbs energies

A system in a thermal equilibrium with its surroundings at a temperature T. When a change in the system occurs and there is transfer of energy as heat between the system and the surroundings, the Clausius inequality, dS - dq/T 0 When the heat transfer occurs at constant volume, dqv = dU dS - dU/T 0 It expresses the criterion for spontaneous change solely in terms of the state functions TdS dU This expression becomes dSu,v 0 (constant internal energy, dU = 0) At constant volume and constant internal energy the entropy increases in a spontaneous change. dUs,v 0 (constant entropy, dS = 0) If entropy and volume are constant, the internal energy must decrease in a spontaneous change. When heat is transfer at constant pressure and there is no work other than expansion, dqp = dH TdS dH (constant P, no non -expansion work) At either constant enthalpy or connnnnnnnstant entropy, this inequality becomes dSH ,p 0 dHs,p 0 Eqn 6.11 and 6.12 have the forms dU - TdS 0 and dH - TdS 0 6.12 6.11

From these equations two thermodynamics quantities can be introduced: Helmholtz energy, A, and Gibbs energy, G A = U TS G = H TS When the state of the system changes at constant temperature dA = dU TdS dG = dH TdS The criteria of spontaneous change as dAT,V 0 dGT,P 0 and the criterion of equilibria is dAT,V = 0 Maximum work The system does maximum work when it is reversibly. TdS dq From the first law dU = dq + dw 6.15 6.16 6.13 6.14

dU TdS + dw or dw dU - TdS

The maximum energy that can be obtained from the system as work dwmaks = dU - TdS At constant temperature dA = dU - TdS dwmak = dA The change in the Helmholtz is equal to the maximum work. For macroscopic isothermal change where wmak = A A = U - TS 6.18 6.19 6.17

6.8

Tenaga bebas Gibbs

At constant temperature and pressure the maximum non-expansion work we,max is given by the change in Gibbs energy. H = U + PV dH = dU + d(PV) When the change is reversible dw = dwrev dq = dqrev = TdS dG = TdS + dwrev + d(PV) - TdS = dwrev + d(PV) dG = (-PdV + dwe,rev ) + d(PV) = dwe,rev + VdP At constant pressure dG = dwe,rev Standard molar Gibbs energy Go Standard entropies and enthalpies of reaction can be combined to obtain the standard Gibbs energy of reaction Gr o . Gr o = Hr o - TSr o 6.20

The standard Gibbs energy of formation is the standard reaction Gibbs energy for the formation of a compound from its elements in their reference state. Gr o = Gf o - Gfo products reactants 6.21

6.9

Combining the first and second laws

The first law

dU = dq + dw

For a reversible change in a closed system of constant composition and in the absence of any non expansion work, dwrev =- PdV dqrev = TdS Therefore dU = TdS - PdV 6.22

Properties of the internal energy U = U (S,V)

U U dU = dV + dS V S S V U = P V S U =T S V
6.10 From dU is exact, therefore The Maxwell relation dU = TdS - PdV

T P = V S S V
This relation is one of the examples of Maxwell relation.

6.23

Properties of the Gibbs energy When the system undergoes a change of state, G may change because H, T and S change. The Gibbs energy G = H -TS For infinitesimal changes in each property dG = dH - TdS - SdT and H = U + PV dH = dU + PdV + VdP For a closed system doing non-expansion work, dU can be replaced by dU = TdS - PdV dG = (TdS - PdV) + PdV + VdP - TdS - SdT dG = VdP - SdT dG is exact differential 6.24

 G = V, P T G = S T P
The Maxwell relation

6.25

V S = T P P T
6.11 The temperature dependence of Gibbs energy

6.26

The equilibrium composition of a system depends on Gibb free energy. It is necessary to know how G varies with temperature. From G = H - TS

S = H -G T

but

G = S T P GH G = T T P

G 1 G d 1 T T = T T + G dT T P P 1 G G 2 T T P T 1 G G T T T P H G = 2 T T P

= =

6.27

This expression is called Gibbs-Helmholtz equation. This equation is useful when it is applied to change, physical and chemical at constant pressure.

G = G Gi f

H (G / T ) = T2 T P
6.12 The pressure dependence of the Gibbs energy

6.28

From

dG = VdP - SdT

When T is constant ,

dT = 0 dG = VdP

G( Pf ) G( Pi ) = VdP = V ( Pf Pi )
Pf Pi

6.29

For a liquid or solid the volume changes only slightly as the pressure changes, For molar quantities

Gm(Pf ) - Gm(Pi) = Vm (Pf - Pi) Gm(Pf ) = Gm(Pi) + Vm P

6.30

The molar volume s of gases are large. Gibbs energy depends strongly on the pressure.

V = nRT/P

G( Pf ) = G( Pi ) + nRT
o

Pf

Pi

dP P
6.31

= G(Pi) + nRT ln (Pf /P i) If Pi = P (standard pressure of 1 bar), the Gibbs energy for perfect gas G(P) = Go + nRT ln (P/P o)

6.32

6.13

The chemical potential of a pure substance

The chemical potential of a pure substance is defined as,

G = n T , p

6.33

10

The chemical potential shows how the Gibbs energy of a system change as a substance is add ed to it. For pure substance, the gibbs energy is

G = n x Gm

6.34

nGm = = Gm n T , P
The chemical potential is the same as the molar Gibbs energy. Perfect gas The chemical potential of perfect gas at a pressure P is = o + RT ln P/Po where o is the standard chemical potential. 6.35

Real gas For real gas the true pressure P is replaced by an effective pressure, called the fugacity, f. = o + RT ln f/Po

6.36

The relation between fugacity and pressure is f = P where is fugacity coefficient. As the pressure approach zero = o + RT ln (P)/Po = o + RT ln P/Po + RT ln 6.38

6.37

11