Lecture MMC301 Up To 05-09-2023 PDF
Lecture MMC301 Up To 05-09-2023 PDF
Lecture MMC301 Up To 05-09-2023 PDF
Kinetics (MMC301)
Where V is the molar volume of the gas at the particular instant indicated in Figure 1.
Suppose that the reversible compression process was carried out from an
initial thermodynamic state designated 1 to a final state designated 2.The
path of the process is depicted by a curve on the P-V diagram (Figure 2)
that joins the end points 1 and 2.
The small shaded strip under the curve represents the work done W = P dV.
𝑽
For the entire process stretching from 1 to 2, we have 𝑾 = 𝑽𝑑 𝑃 𝟐 𝑽..........(3).
𝟏
Heat flows from the system to its surroundings, or vice versa, by virtue of a temperature difference, however
small, between the system and the surroundings.
The convention is that the heat is positive when it is absorbed by the system from the surroundings and negative
when heat is lost by the system to do the surroundings.
In adiabatic processes, no heat is exchanged between the system and its surroundings. In other words, Q = 0 for an
adiabatic process.
W is dependent on the path taken by the system between two given thermodynamic States.
Similarly, Q is not a state function either, that is ,it can not be expressed as a function of the thermodynamic
coordinates (P, T, etc).
FIRST LAW OF THERMODYNAMICS
The statement of the law of conservation of energy.
E = Q W ……………. (1)
Q and W are not state functions, but their difference Q W = E is a state function.
In other words, E can be expressed as a function of thermodynamic variable such as P,T and so forth.
In this particular cycle, steps 1 and 3 are constant volume steps and 2 and 4 are constant pressure steps.
Therefore, (E)cycle = 0
The first law applies whether the process is reversible or not. For an infinitesimal process, the
first law statement can be expressed as follows: dE = Q W
REVERSIBLE AND IRREVERSIBLE PROCESSES
Reversible process:
A process is said to be reversible if it is performed in such a way that at the completion of the process, both the system and its
surroundings can be restored to their respective initial states. Because the system and the surroundings together constitute the
universe, it is clear that a reversible process is one that is performed in such a way that the universe is not able altered.
Reversible isothermal process:
The reversible isothermal process that is carried out reversibly keeping the temperature constant.
Reversible adiabatic process:
A reversible adiabatic process is carried out reversibly with the system thermally insulated from the surroundings.
The adiabatic free expansion of an ideal gas into an evacuated vessel in a typical example of an irreversible process.
For work to be done, the gas should expand against an opposing force
that is very nearly equal to the force exerted by the gas on the face of the
piston. In this example, the external force is either nil or substantially
less than the force exerted by the gas. The evacuated compartment offers
no resistance.
W = 0 and W = 0, and Q = 0 (as the process is adiabatic)
Q = E + W = 0 or E =0
Examples of irreversible process are i. Spontaneous flow of heat from a
system to cooler surroundings, ii. spontaneous chemical reaction, iii.
Spontaneous solidification of a super cool liquid metal and iv. Mixing of
substances to form a homogeneous solution .
HEAT AND WORK CHANGES IN REVERSIBLE PROCESSES:
ISOTHERMAL PROCESS:
This is for 1 mole of gas. If the system consists of n moles of ideal gas, then W = nRT0 ln(V2/V1) = n RT0 ln(P1/P2)
Q = W = RT0 ln(V2/V1), As E = 0 for an ideal gas.
2 2
W = 1 𝑃𝑑𝑉 = 𝑃 1 𝑑𝑉 = 𝑃(𝑉2 − 𝑉1)
The heat exchanged, Qisobaric or QP , can readily be determined by applying the first law of thermodynamics:
Where H, a new state property, known as the enthalpy (or heat content) is defined as follows: H = E + PV
For condensed phase, the product PV is rather small and for these substances H E.
For a constant pressure process, QP = enthalpy change, HP and QP = dHP
For a constant volume process, QV = internal energy change, EV and QV = dEV
𝐶𝑃 = 𝛿𝑄𝑃 𝑑𝑇𝑃 = 𝜕𝐻 𝜕𝑇 P
𝐶𝑉 = 𝛿𝑄𝑉 𝑑𝑇𝑉 = 𝜕𝐸 𝜕𝑇 V
Heat capacity can be expressed in calories or joules per degree kelvin or in Btu per degree Rankine. Molar heat capacity, C , is
heat capacity per mole.
The heat capacity of a substance is markedly influenced by temperature. At low temperature, CP approaches CV and at
temperature nearing absolute zero, both CP and CV tend to zero. At higher temperature, the Dulong and petit rule gives a
reasonable estimate of the heat capacity. According to this rule, the heat capacity of a solid approaches a value of 3R or 24.94
J/g.atom.K at high temperature.
LOW TEMPERATURE HEAT CAPACITIES:
The Debye theory of heat capacities provides a useful framework to analyzing low-temperature heat capacity data. Debye
equation is as follows: CV =𝐾 𝑇 3 Where K is a constant equal to 1944 J/g.mole.K and is known as Debye temperature.
Limitation: The Debye equation neglects the electronic contribution to the heat capacity. This contribution is quite significant
for metallic substances.
The modified equation for heat capacity at low temperature is CV =𝐾 𝑇 3 + T …………… (1)
both and can be determined from low temperature heat capacity measurements. On dividing both sides of equation(1) by
T we have CV /T= 𝐾 𝜃 3 𝑇 2 + 𝛾
A plot of CV/T versus T2 yields a straight line with a slope equal to K/3 and the intercept at T2 = 0 gives the value of .
where a, b and c are empirical constants to be determined from experimental measurement of CP.
On the other hand, Kelley prefers a slightly different relationship
CP = a + bT - cT2 J/g.mole.K.
Relationship between CP and CV for an ideal gas
The heat capacity at constant volume is 𝐶𝑉 = 𝜕𝐸 𝜕𝑇 𝑉 ………….. (1)
For an ideal gas, E is solely a function of T and independent of both P and V . Accordingly, for an ideal gas
𝑑𝐸
𝐶𝑉 = 𝑑𝑇 = 𝜕𝐸 𝜕𝑇 𝑃 = 𝜕𝐸 𝜕𝑇 𝑉 …………… (2)
As H = E + PV …… (4)
𝜕𝐻 𝜕𝑇 𝑃 = 𝜕𝐸 𝜕𝑇 𝑃 + 𝑃 𝜕𝑉 𝜕𝑇 𝑃 ………. 5
𝐶𝑃 = 𝐶𝑉 + 𝑃 𝜕𝑉 𝜕𝑇 𝑃 ………. 6
𝑅
For an ideal gas, PV = RT 𝜕𝑉 𝜕𝑇 𝑃 = 𝑃 … … … . (7)
𝑅
Hence 𝐶𝑃 = 𝐶𝑉 + 𝑃 𝜕𝑉 𝜕𝑇 𝑃 = 𝐶𝑉 + 𝑃 × 𝐶𝑃 − 𝐶𝑉 = 𝑅
𝑃
CALCULATION OF ENTHALPY CHANGES
The enthalpy change associated with change in temperature of a substances can be calculated from the heat capacity data a
follows.
𝑇
At constant pressure dH = CP dT On integration H = 𝑇2 𝐶𝑃 𝑑𝑇
2
𝑇 𝑏 1 1
On the substitution for CP, H = 𝑇2(𝑎 + 𝑏𝑇 + 𝐶𝑇 −2 )𝑑𝑇 → ∆𝐻 = 𝑎 𝑇2 − 𝑇1 + 𝑇22 − 𝑇12 − 𝑐 −𝑇
2 2 𝑇2 1
Gases: For gases elements and compounds, pure, ideally behaving gas at 1 atm pressure and specified temperature is the
standard state.
T1
Differential form of Kirchhoff’s law 𝑑∆𝐻 𝑑𝑇 𝑃 = ∆𝐶𝑃 …… (6) C P C P , products C P ,reac tan ts
Problem
Find the H0 at 1200 K for the following reaction
Fe2O3 (S) + 3 CO (g) = 2 Fe(s) + 3CO2 (g)
Following data are given
Transformation Transformation Heat of transformation (J)
temperature (K)
Fe2 O3 ,1053 Fe2 O3 ,1053 : H 5 Fe2 O3 ,1053 Fe2 O3 ,1200 : H 6 2Fe ,298 2Fe ,1033 : H 7
2 Fe ,1033 2Fe ,1033 : H 8 2Fe ,1033 2Fe ,1187 : H 9 2Fe ,1187 2Fe ,1187 : H10
2Fe ,1187 2Fe ,1200 : H11 3Cog,298 3Cog,1200 : H12 3Co2 g ,298 3Co2 g ,1200 : H13
For the reaction at 1200K, Fe2 O3 ,1200 3Cog ,1200 2Fe ,1200 3Co2 g ,1200
H 1 H 298
0
27700 J
C
3 2
H 2 P Fe2 O3 dT 5
298 298
For the ideal gas, E is a function of T only. Therefore, the partial deviation of E with respect to T can be replaced by the
𝜕𝐸 𝑑𝐸
total deviation . 𝐶𝑉 = 𝜕𝑇 𝑉 = 𝑑𝑇 → 𝑑𝐸 = 𝐶𝑉 dT for ideal gas
d ln V CV
d ln T
R
d ln V CV
d ln T 0
CR
d ln V V .T 0
On integration: 𝑉 𝑅 𝐶𝑉 𝑇 = 𝑘 … … . . (3)
R CP R
1 1.......(4) as CP –CV = R
CV CV CV
R
Let us suppose, that the initial and final states of the system are (P1, V1, T1) and (P2, V2, T2) respectively. An integrating
equation (6). 1−𝛾 1−𝛾
𝑊 = 𝐶 Τ 1 − 𝛾 𝑉2 − 𝑉1 … … . . (7)
𝛾
𝐴𝑔𝑎𝑖𝑛, 𝐶 = 𝑃2𝑉2𝛾 = P1𝑉1 =P𝑉 𝛾 … … … … … … … … . (8)
On combining equation (7) and (8) we obtain W = (P1V1 – P2V2)/( - 1) …………. (9)
CV T2 T1 Q
P1V1 P2V2
n 1
We know that CP – CV = R CP/CV – 1 = R/CV CV = R/( - 1) [As CP/CV = ]
Heat exchanged
Q
R
T2 T1 R .T1 T2
1 n 1
1 1
Q RT1 T2
n 1 1
Q
R
T1 T2 n W . n
n 1 1 1
Problem
Air (ideal gas with = 1.4 ) at 1 bar and 300K is compressed till the final volume is one-sixteenth of the original volume,
following a polytrophic process PV1.25 = constant.
Calculate (a) The final pressure and temperature of the air, (b) Work done and (c) The energy transferred as heat per mole of air.
Solution:
(a) Initial volume V1, and final volume V2
V2 T1 T2
2
P1V1
1
1 16 V1
n 1.4 1.25
(c) Q W 9.977 3.741 KJ mole
1 1.4 1
Problem
Calculate the heat lost to the surrounding when 1g sphere of zinc sulphide is roasted to zinc oxide at 900⁰K. The following dada
are given:
Hf0 at 298K (kcal) CP (cal/g.mole.K)
ZnS (S) 49.05 12.16 + (1.24 × 103 T) – (1.36 × 105 × T2)
ZnO (S) 83.80 11.71 + (1.22 × 103 T) – (2.18× 105 × T2)
O2 (g) 0 7.16 + (1.0 × 103 T) – (0.4 × 105 × T2)
SO2 (g) 70.94 10.38 + (2.54 × 103 T) – (1.42 × 105 × T2)
For reaction (1) C P 11.71 10.38 12.16 1.5 7.16 1.22 10 2.54 10 1.24 10 1.5 10 T
3 3 3 3
2.18 105 1.42 105 1.36 105 0.6 105 T 2
C P 0.81 1.02 10 3 T 1.62 105 T 2 cal g.mole. K
H 900
0
105690 488 368 182 550 106178cal
This figure represented that amount of heat lost when 1g.mole ZnS is roasted at steady state.
Note:
In this problem it is implied that the reactants, ZnS and O2 as well as the products ZnO & SO2 are at a steady
state temperature of 900⁰K.
It is also clear that maintenance of the steady state condition require that all heat generated by the roasting
process be delivered to the surrounding.
SECOND LAW OF THERMODYNAMICS
The first law of thermodynamics essentially and generalization of the principle of conservation of energy.
Prolonged
period of time
Work can be converted completely into heat, the reverse is not true with the help of a suitable device.
The second law, on the other hand, is capable of expressing the inherent limit to the efficiency of converting heat into work
Sadi Carnot (1796-1832), one of the outstanding workers in the history of thermodynamics, intensively studied the
fundamental reasons for the inherent limit to the efficiency.
The Clausius statement of the second law: No process is possible whose sole result is the transfer of heat from a colder body
to a hotter body.
The Kelvin-Plank statement of the second law: no process is possible whose sole result is the complete conversion of heat into
work.
EFFICIENCY OF A HEAT ENGINE
A heat engine is a device that converts heat into work.
The heat engine uses working substances (i.e. ideal gas, real gas, steam etc) and suffers no
permanent change during operation.
The working substances a system is taken through a series of processor that together from a cycle
the heat engine will absorbed heat during one part of the cycle, convert a portion of it into work
and reject the reminder during another part of the cycle.
No heat engine is 100% efficient, because a portion , however small, of the heat is observed is always
rejected
Where Q2 is positive (because heat is absorbed by the system) and Q1 is negative (because heat is rejected by the system)
Q1
1
Q2
The Carnot cycle
One of the most important cyclic processes is the Carnot cycle, first described by Sadi Carnot in 1824.
E A CV (T2 T1 )
The work done is given by WA E A CV (T2 T1 )
Further more for an adiabatic process, T1V1 1 T2V2 1 where C P CV Figure: The Carnot cycle shown in P-
V coordinates
T2 T1 V1 V2 ...............(1)
1
Step B: The insulation jacket is removed and the system is contact with the high temperature reservoir at T2. It is allowed to
exposed isothermally and reversibly. Heat is absorbed by this system during the expansion and useful work is done on the
surrounding
EB = 0 (ideal gas), WB RT2 ln V2' V2 and QB Q2 WB RT2 ln V2' V2
Step C: The system is taken out of contact with the high temperature reservoir and is insulated it is allowed to expand
adiabatically and reversibly unit 1 the temperature of the system decline to T1
QC 0, EC CV T1 T2 and WC EC CV T1 T2
Wnet RT2 ln V2' V2 RT1 ln V1 V1'
Wnet RT V V RT ln V V
2 2
'
2 1 1
'
1
Wnet RT ln V2' V2 T2 T1 Q2 Q1
Wnet
Q2 Q1 R ln V2' V2 T2 T1
T2 T1 T2
The efficiency of a heat engine operating on the Carnot Cycle is given by
Q2 Q2 RT 2 ln V2' V1
T1 Q1
1 1 ...........(6 8)
T2 Q2
Carnot Refrigerator
Figure: The Carnot cycle shown in P-V coordinates Figure: Schematic diagram of Carnot Refrigerator
𝑉1′ൗ
𝑄1′ = heat absorbed = 𝑅𝑇1 ln( 𝑉1) = −𝑄1
RT1 ln V1 V1 T1
C Q1 Wnet
R ln V1 V1 T2 T1 T2 T1
The coefficient of performance for a refrigerator, unlike the efficiency of heat engine, can be considerably greater
than unity.
The concept of entropy
The efficiency of a Carnot heat engine operating between a hot reservoir at T2 and cold reservoir at T1 is given by,
T1 Q Q Q
1 1 1 1 2 0...............(1)
T2 Q2 T1 T2
All four steps in the Carnot cycle are reversible. Thus, the heat from appearing in equation (1) refer to heats exchanged in
reversible process.
Q1,r Q2,r
0..............(2)
T1 T2
Where the subscript r denotes a reversible process. This can be written as Qi ,r Ti 0.......(3)
Suppose we have consider a Carnot cycle in which T1 and T2 differ by only an infinitesimal amount. In such a cycle, Qi,r
represents the heat exchanged reversibly at temperature Ti.
Q3,r Q4,r
For the Carnot cycle efgh 0
T3 T4
The quantity 𝛿𝑄𝑟ൗ𝑇 has the attributes to state property. Its value does not change in a cyclic process and any change occurring in
it during a process is independent of the process path and depends only on the initial and final states of the system. The
quantity 𝛿𝑄𝑟ൗ𝑇 is designated dS, where S is a new thermodynamics quantity call entropy.
Qr
dS ........................(3)
T
dS 0..............................(4)
cycle
A system undergoes a change from an initial thermodynamic state (P1, V1, T1) to a final thermodynamic state (P2, V2, T2), the
2 𝛿𝑄
associated entropy change is given by ∆𝑆 = 𝑆2 − 𝑆1 = 1 𝑇 𝑟
where S1 and S2 are determined solely by the state variable.
𝑄2,𝑟 𝑉2
The entropy change, ∆𝑆 = σ ∆𝑆 = 𝑅 𝑙𝑛
𝑇 𝑉1
(3) Reversible isochoric or isovolumic process:
In such a process, no work is done and the heat exchanged is given by 𝛿𝑄𝑟 = 𝑑𝐸 = 𝐶𝑉 𝑑𝑇
𝛿𝑄𝑟
By definition 𝑑𝑆 = = 𝐶𝑉 𝑑𝑙𝑛𝑇
𝑇
If a system is subjected to an isochoric process defined by the initial state (P1, V1, T1) and (P2, V1, T2) the final state the
entropy change would be ∆𝑆 = 𝑇𝑛𝑙 𝑑 𝑉𝐶 = 𝑆𝑑
𝑇2
If CV is independent of temperature ∆𝑆 = 𝐶𝑉 𝑙𝑛 𝑇1
For the process defined by the initial state (P1, V1, T1) and final state (P2, V1, T2) the final state.
∆𝑆 = 𝑆2 − 𝑆1 = න 𝐶𝑃 𝑑 ln 𝑇
𝑄𝑟 ∆𝐻𝑚0
Entropy of fusion = 0
∆𝑆𝑚 = =
𝑇𝑟 𝑇𝑚
Example: Copper melts at 1083⁰C and its heat of fusion is 12970 J/mole. Calculate the entropy of fusion of copper.
304400
S v0 106.9 J mole. K
2848
Solid iron can exit in three different allotropic modifications, for example, face-entered-cubic γ-iron is transformed to body-
cantered-cubic δ- iron at 1391⁰C. The transformation of γ- iron to δ- iron at 1391⁰C, the so called transition temperature. Tf , is
accompanied by absorption of heat. The transformation occurs at constant temperature and constant pressure.
Temperature of transformation = Tf
S 0f H 0f T f
(8) Entropy changes in some irreversible process:
a. Free expansion of an ideal gas: This is an irreversible adiabatic process. (P1, V1, T1) represents the initial state and (P2, V2,
T1) denotes the final state after free expansion( as indicated earlier, the temperature of an ideal gas remains unaltered during
free expansion).
To calculate the entropy change associated with process we consider a single reversible process as a combination of reversible
process whose net result is to induce the same changes as the irreversible process.
A reversible isothermal process from (P1, V1, T1) to (P2, V2, T1) produces the same changes in the state variables as does
free expansion
A combination consisting of a reversible isobaric process followed by a reversible isochoric (isovolume) process can also be
used to simulate the given free expansion process.
In the free-expansion process, although no heat is exchanged, there is a net gain in the entropy of the system.
Liquid metal can be super cooled to temperature considerably below their normal solidification temperatures.
Solidification of such liquids occurs spontaneously ( or irreversibly).
1g.mole of liquid silver that has been super cooled to 940⁰C is the system under consideration. The super cooled liquid is
allowed to solidify at 940⁰C.
Sirreversible = ?
The calculation is facilitated by constructing reversible cycle path between the
initial and the final state of the system. Such a reversible cyclic path, consist of
four sub processes, is shown in figure- 1.
I. Heat the super cooled liquid silver reversibly and isobarically to 960.5⁰C (the
normal solidification temperature)
II. Allow solidification of liquid silver reversibly at 960.5⁰C at 1 atm pressure.
III. Cool the solid silver reversibly and isobarically to a temperature at 940⁰C.
IV. Allow melting of the solid silver reversibly at 940⁰C at 1 atm pressure.
Figure 1: A cyclic path consisting
of four subprocesses all of which
SI, SII , SIII and SIV denote the entropy changes associated with the are reversible
four reversible sub processes.
dS 0 S I S II S III S IV 0
S IV S I S II S III .....................(1)
Note that the quantity on the left side of equation-(1) represents the entropy change associated with solidification of
liquid silver at 940⁰C.
The following thermochemical date are taken from Kubaschewski and Alcock
10 5
C Pl liquid silver 30.5 J mole.K
C PS solid silver 21.3 8.54 10 T 1.51 2 J mole.K
3
T
H s0 H m0 11090 J mole
1233.5
Sub process I: dS C Pe T dT S I 30.5 T dT 0.51 J mole. K
1213
1213
Sub process III: dS C PS T dT S III C PS T dT 0.53 J mole. K
1233.5
S 4 9.01 J mole.K
In other words, when super cooled liquid silver at 940⁰C is allowed to solidify at that temperature, its entropy
decreases by 9.01 J/g.mole.K.
Entropy change of the universe in an irreversible process
Incorporation of an irreversible step into a Carnot cycle produces changes in the thermodynamic efficiency and the entropy
of the universe. The conventional Carnot cycle consists of four reversible steps:
Adiabatic compression (A), isothermal expansion (B), adiabatic expansion (C), and isothermal compression (D).
There may be an increase in the entropy of the universe each time the
working substance is taken through the modified cycle. For simplicity, 1
mole of ideal gas is considered as the working substance.
Fig-2(a), at the completion of step B all the gas is on the right of this diagram that separates it from an evacuated chamber on
the left.
After the cylinder and piston are thoroughly insulated, suppose that an opportune moment the diaphragm is ruptured, where
upon the gas rushes into the evacuated chamber.
At the conclusion of step B’, then this gas will occupy the entire space in the cylinder as shown in Figure 2(b).
Because there is no change in the temperature of an ideal gas during an adiabatic free expansion at the completion of step B’
the thermodynamic state of the system is defined as (P3’, V3’, T2).
The remainder the modified cycle consists of two reversible adiabatic (A and C’) and two reversible isothermals ( B & D ).
The entropy change can be calculated by assuming a reversible isothermal process between thermodynamic state 3 and 3′.
....................8
V2 V3 V3 V4
V1 V V2 V1
4
V ln V
R 3
V
An substituting equation (8) into equation (7), we obtain S s R ln R ln
3 1
V V V3
2 4
V V V V V
R ln 3
1
3
R ln 1 3
V2 V V3 V V2
4 4
V V
V3 V4
S S R ln 1 4 R ln 1 0........................(9)
V4 V1
V2 V1
This result is entirely reasonable considering the fact that we are dealing with the entropy change in a cyclic in a process.
By combining equations (8) and (6), we find
V3 V
Wnet RT2 ln RT1 ln 1
V2 V
4
V3 V
RT2 ln RT1 ln 2
V2 V
3
V3 V V
RT2 ln RT1 ln 2 3
V2 V3 V
3
V3 V3 V
RT2 RT1 ln RT1 ln 3
V2 V2 V
3
V3 V
R ln T2 T1 RT1 ln 3 ............................(9)
V2 V3
The efficiency of the modified cycle is given by
R lnV3 V2 T2 T1 RT1 lnV3 V3
Wnet Q2
RT2 ln V3 V2
T2 T1
RT1 ln(V3 V3 ) RT2 ln(V3 V2 )
T2
T1
1 RT1 lnV3 V3 RT2 ln V3 V2 .................................10
T2
Because V3 is greater than either V3 or V2 , the third term on the right hand side is a negative quantity. Hence, it
follows that is less than the Carnot efficiency. The diminution (decrease) in the efficiency of the modified cycle is
directly linked to the presence of the irreversible step B’, the greater the departure of V3 from V3, the longer is
decrease in efficiency.
In order to determine the entropy change of the universe due to the modified cycle, we need to calculate the entropy change of
the surroundings. The higher temperature reservoir “losses” an amount of thermal energy equal to Q2 . The low-temperature
reservoir “grains” an amount of heat equal to Q1’.
V3
R ln ..................11
Q2
Entropy change of high-temperature reservoir =
T2 V2
V
R ln 1 ................................12
Entropy change of the low- temperature reservoir = Q1
T1 V
4
V3 V
Sl R ln R ln 1 ......................................13
V2 V
4
On combining equation (13) with equation (8), we find that
V3 V V V
Sl R ln R ln 2 ......................................14 as 3 4
V2 V V2 V1
3
V V V
S l R ln 3 R ln 2 3
V2 V3
V3
V V V
R ln 3 R ln 3 R ln 3
V2 V2
V3
V
R ln 3
V3
Because V3’ is greater than V3, this quantity is positive the entropy change of the universe is given by
V
Su Sl R ln 3 .......................15
V3
It can be said that the presence of an irreversible step in an otherwise reversible cyclic process will reduce the efficiency of a
heat engine operating on the cycle, furthermore, there will be an increase in the entropy of the universe each time the cycle is
completed.
Equation (9) and (15) can now be combined into a single expression Su 0 or dSu 0 ………….. (16)
The clausius inequality
The efficiency of a heat engine operating on a modified cyclic process containing an extra irreversible step is less than the
Carnot-cycle efficiency.
RT ln V V
T1 3
Q2 Q1
...........................17
1 3
1
T2 RT2 ln V3 V2
Q2
T Q
Because V3’ V3 V2 it is clear that 1 1 2 Q Q Q '
T
1
0 2
1
2 Q2 T2 T1
It is important to note that Q2 and Q1 are the heat exchanged reversibly by the system with the surroundings.
Q2,r Q1,r
For the cyclic process containing are irreversible step 0 Qi ,r Ti 0...............(18)
T2 T1
For the strict Carnot cycle consisting of four reversible step, Q i ,r Ti 0.............................19
Equations (18) and (19) can be combined to yield the following general expression:
Q i ,r Ti 0.............................20
In other words, wherever a system is taken around a cycle consisting of several steps, the sum of the heat exchanged
reversible Qi,r divided by the reservoir temperature, Ti for each step is less than equal to zero. This known as the
Clausius in equality.
The usefulness of the first law equation (4) is severely limited by the fact that is not a complete differential, that it is
dependent on the both of the process. This short coming can be overcome by combining this relationship with the second law
statement. According to the second law, for a reversible process spanning two equilibrium states, the entropy change , dS, is
equal to the heat exchanged, Qr, divided by this temperature, T.
Qr
dS Qr TdS ...............................5
T
It is clear that for any reversible process involving only mechanical work,
For the general case in which several different terms of work are involved,
TdS dE PdV
dE P
dS dV
T T
Considering E and V as function of T and P
E E
dE dP dT ............................................1
P T T P
V V
dV dP dT ............................................2
P T T P
Substitution gives E
1 E P V V
dS dP dT dP dT
T P P T P T P T T P
1 E V 1 E V
P dP P dT ...........................3
T P T P T T T P T P
Expressing S as a function of P and T
S S
dS dP dT ............................................4
P T T P
S 1 E V
P ...........................................5
P T T P T T T
S 1 E V
P ...........................................6
T P T T P T P
2S 1 2E 2V 1 E V
P 2 P ..............................7
TP T TP TP T P T P T
2S 1 2E 2V V
P ..............................8
PT T TP TP T P
The mixed second-order differentials S appearing on the left side of the equation (7) and (8) are equal.
1 2E 2V 1 E V 1 E
2
2V V
P 2 P P
T T P T P
T P T P T
T T P T P T P
1 E V 1 V
0 2 P
T P T P T T T P
1 E V 1 V
0 2 P
T P T P T T T P
1 E V V
P
T P T P T T P
E V V
T P .................................9
P T T P P T
E V V
P T .................................10
P T P T T P
S 1 E V
From equation (5) and (10) P .........................................5
P T T P T P T
S V
......................................11
P T T P
From equation (6) S 1 E V
P
T P T T P T P
1 E PV 1 H
.............................12
T T P T T P
V 1 H
As a result we have dS dP dT .....................................13
T P T T P
From the definition of CP , the heat capacity at constant pressure, we note that
1 H C
P
T T P T
We can now define a quantity called the coefficient of thermal expansion, , as follows
1 V
.....................(14)
V T P
Thus, is the volume change per unit volume per degree change in temperature at constant pressure.
V
V
T P
C
dS VdP P dT .......................................15
T
V
TdS C P dT T dP........................................16
T P
1 E 1 E
dS P dV dT .................................18
T V T
T T V
Because dV and dT are independent, comparison of the coefficient of these deferential yields.
S 1 E
S 1 E ...................................................20
P ...................................................19 T V T T V
V T T V T
2S 1 2 E P 1 E
P ............................21
TV T TV T V T 2 V T
Differentiating equation (20) with respect to V at constant T
2S 1 2E
....................(22)
VT T VT
Setting equation (21) and (22) equal and cancelling the mixed second-order differentials,
1 E P 1 E 1 2E
2
V 2 P . T
T TV T V T V T T VT
1 P 1 E
0 2 P
T T V T V T
E P
P T ............................................................23
V T T V
S P
As a result ..............................24
V T T V
S 1 E E
.....................25
C
and V As C
V T T T V T
V
T V
P C
Put the value equation in (17) dS dV V dT ..................................26
T V T
The partial differential 𝜕𝑃Τ𝜕𝑇 𝑉 can be expressed in terms of measurable quantities like the coefficient of thermal
expansion and isothermal compressibility. Later its defined as follows
1 V
Isothermal Compressibility ...............................27
V P T
is defined on the change in volume per unit volume per unit change in pressure under isothermal conditions are dividing
coefficient of thermal expansion (equation 14) with isothermal compressibility (equation (27))
1 V
V T P
1 V V
P P ................................28
V T T
1 V V
V P T P T
Let us consider a constant volume process, for which equation (2) reduce to
V V
dV dPV dTV 0...............................29
P T T P
The subscript V indicates that the changes occur in a constant volume process. Rearranging term in equation (29).
V V
dPV dTV
P T T P
V
dPV P T P ....................................30
dTV T V V
P T
P
Comparing equation (28) and (30), we obtain .................................31
T V
C P
Substitute equation (31) into equation (27) dS V dT dV
T T V
C
V dT dV ..........................................32
T
T
TdS CV dT dV .........................................33
(3) P and V are chosen as independent variables
S 1 E
.....................................34
P V T P V
S 1 E
P.....................................35
1
V P T V P T
S C T C
V V ..........................36
P V T P V T
S C T C
V V ..........................37
V P T V P TV
T T
TdS CV dP C P dV .................................38
P V V P
Problem
Calculate the coefficient of thermal expansion and isothermal compressibility for an (a) Ideal gas (b) a Van der Waals
gas. By defining
1 V 1 V
and
V T P V P T
Solution
(a) For 1 mole of an ideal gas, the equation of state is PV = RT
1 V
V T P
V R 1
.
1 R
T
PV
R
T P P V P R PV T
R 1
VR T
V RT
2
P T P
T
RTV 3 2aV b
2
V P RV 3 V b
Again V
1 V
RV 3 V b
T P T P RTV 2aV b
3 2
T
V P
Substitute in equation of 1 V 1 RV 3 V b
2
V T P V RTV 3
2a V b
RV 2 V b
2
RTV 3
2a V b
P
To find the value of , we make use of equation
T V
P R
V V V b
V b
R
RV V b V b
2
RTV 3 2aV b
2
V
V b
22
RTV 3 2aV b
2
Difference between heat capacities CP and CV
E V
C P CV P ..............................................1
V T T P
E P
Again we derived P T
V T T V
P V
C P CV T ..............................................2
T V T P
1 V
Again coefficient of thermal expansion
V T P
1 V
and isothermal compressibility
V P T V R
T P P
For 1mole of ideal gas PV = RT 1 R 1
V P T
V RT
2
P T P
1 RT 1
2
V P P
V P
V and
T P T V
T 2V
C P CV TV .
1 PV 1 1
C P CV TV .P and
T2 T T P
The measured values of CP, CV and for monatomic gases at room temperature are in good agreement with those
values. For a diatomic gas, the values of CV, CP and are 5/2 R, 7/2R and 1.40, respectively.
Problem: Show that for an ideal gas the internal energy is solely function of temperature
Solution:
Because the internal energy E is a state function, it can be expressed as a function of state variables such as V and T.
E E
E = f(V, T) and dE dT dV
T V V T
E P
P T
V T T V
E P
T P
V T T V
P R
For 1 mole of an ideal gas, PV = RT. Differentiating at constant volume
T V V
E TR TR
P0 here P
V T V V
E E
dE dT CV dT as CV E = f(T) for an ideal gas
T V T V
Entropy of an ideal gas
From useful thermodynamic correlation T and P are independent variables.
Let us begin with equation according to the equation for 1 mole of an ideal gas
V dT V
TdS C P dT T dP dS C P dP.................................1
T P T T P
Let Sr, Pr and Tr denote the entropy, pressure and temperature of the substance in a reference state. Frequently Tr = 298 K
and Pr = 1 atm defined the chosen reference state integration of equation yields.
S T P V
Sr dS Tr P
C d ln T Pr T P dP
T P V
S S r C P d ln T dP
Pr T
Tr
P
P V
dP.........................2
T
S S r C P d ln T
Pr T
Tr
P
This gives the entropy as a function of temperature and pressure to calculate the entropy as a function of T and V .
C
dS V dT dV
T
For an ideal gas, = 1/T and = 1/P, thus / = P/T = R/V [As PV = RT P/T = R/V]
dV
dS CV d ln T R CV d ln T R ln V
V
T V
S S r CV ln R ln ........................................4
Tr Vr
T T
TdS CV dP C P dV
V
P V P
CV T C T
dS dP P dV
T P V T V P
CV C
. dP P dV
T TV
C T CP
V dP dV
T P 1
TV
T
CV d ln p C P d ln V
P V
S S r CV ln C P ln .................................6.97
Pr Vr
Absolute value of entropy of a substance
The absolute value for entropy, unlike that for enthalpy or internal energy can be determined. There are numerous stand
order compilations, such as that by kubaschewski and Alcock, listing absolute entropy values for substances at a standard
temperature of 298.15K (or 298⁰K, for short). The entropy change under isobaric condition the equation is expressed as
CP
dS VdP dT
T
For isobaric dP = 0
CP S 0
P ........................................1
C
dS dT
T T P T
CP
dS 0 dT
T
CP
dT ..............................................2
298
0
S 298 S 00
0
T
The degree sign denotes standard state at 1 atm. Here, S00 denotes the entropy of the substances at absolute zero. The
quantity of the left side of equation (2) that is the difference between the entropies at 298⁰K and 0⁰K. It Can be determined
by contracting a plot CP/T against T and then measuring the area under the curve. If we put S00= 0
dT ..................................3
298 CP
S 0
298
0 T
At low temperature, specially near absolute zero, data on heat capacities are lacking for many substances. This lack of data
is overcome by making extrapolations to lower temperature. In this regards, this following relationship for heat capacities
CP has proved useful at low temperature.
C P aT 3 T CV .........................................4
Where a and are constants. Over this range of applicability of equation (4), the entropy ST0 at T can be obtained from
equations (3) and (4).
ST0 aT 3 T
dT
T
aT 3
S T ..............................................5
0
T
3
Over the range of validity of equation (4), because is small, the entropy ST0 at TK tends to be less than CP at the same
temperature. At low temperature, (but not T < 1K), can be neglected and
T 3 CP
S a
0
T ............................................6
3 3
With equation (6), the extrapolation down to 0⁰K is not satisfactory, because deviations occur from observations in the
range T < 1K.