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Thermodynamics

by Enrico Fermi

John L. Weatherwax

August 1, 2014

Introduction

Here youll find some notes that I wrote up as I worked through this excellent book. Ive

worked hard to make these notes as good as I can, but I have no illusions that they are perfect.

If you feel that that there is a better way to accomplish or explain an exercise or derivation

presented in these notes; or that one or more of the explanations is unclear, incomplete,

or misleading, please tell me. If you find an error of any kind technical, grammatical,

typographical, whatever please tell me that, too. Ill gladly add to the acknowledgments

in later printings the name of the first person to bring each problem to my attention.

Acknowledgments

Special thanks to (most recent comments are listed first): Neill Warrington, Eduardo Becerra,

Giacomo Caria, Rosario Oliva, Juanico Loran, Glenn Musano, and Don Rintala for helping

improve these notes and solutions.

All comments (no matter how small) are much appreciated. In fact, if you find these notes

useful I would appreciate a contribution in the form of a solution to a problem that is not yet

worked in these notes. Sort of a take a penny, leave a penny type of approach. Remember:

pay it forward.

wax@alum.mit.edu

Addendums/Clarifications/Derivations

Constraints on Motion in the p-V plane (Page 6)

Note that in general, there is no conditions or requirements on the motion of a piston in

connection with the gas to which it is attached. What this means is that without any other

information the path in (V, p) can be taken arbitrary and simply represents the projection

of points in (V, p, T ) space onto the (V, p) plane. The only requirement is that at every

(V, p) point the gas is assumed to be in equilibrium and must satisfy its equation of state

f (p, V, T ) = 0. In this way the temperature T maybe computed if desired.

If we are told more information about the specific type of path in the (V, p) plane (like in fact

that it is along an isentrope or an isotherm) then the path in the (V, p) plane is completely

specified by its two endpoints.

done during an Isothermal Expansion (Page 9)

Now p1 and p2 are the initial and final pressures for m grams of an ideal gas under an

isothermal expansion. As such evaluating the ideal gas law at the two end points gives

m

p1 V 1 =

RT

(1)

M

m

RT

(2)

p2 V 2 =

M

where T the common temperature. Dividing these two expressions we have

p1 V 1

=1

p2 V 2

(3)

p2

V1

=

.

V2

p1

(4)

It is because of this relationship that we have the equivalence of the two work expressions

given in Fermi Eq. 10 from the book.

T and p (Page 20)

The first law of thermodynamic in terms of its canonical variables U and V is given by

dU + pdV = dQ .

To express this in terms of the independent variables T and p we first express the differential

of internal energy U in terms of these variables (using standard calculus) as

U

U

dU =

dp +

dT .

(5)

p T

T p

In the same way, we next express the differential of V in terms of the variables T and p as

V

V

dp +

dT .

(6)

dV =

p T

T p

These two expressions are then inserted into the left hand side of the first law of thermodynamics (replacing dU and dV ) giving

"

#

U

V

V

U

dp +

dT + p

dp +

dT = dQ .

(7)

p T

T p

p T

T p

Now grouping dp and dT terms we obtain

U

p

+p

T

V

p

dp +

"

U

T

+p

V

T

#

dT = dQ .

(8)

CV (Page 24)

Now Fermi Eq. 30 is

CV dT + pdV = dQ ,

(9)

and taking the differential of the ideal gas law gives (Fermi Eq. 31) or

pdV + V dp = RdT .

(10)

CV dT V dp = dQ RdT ,

(11)

(CV + R)dT V dp = dQ .

(12)

This is Fermi Eq. 32. Now a transformation at constant pressure has dp = 0 (by definition)

and remembering the definition of Cp

dQ

,

Cp

dT p

Cp =

dQ

dT

= CV + R .

(13)

Which is Fermi Eq. 33. As described in the text this same expression can be obtained for a

ideal gas in the following way. Since for an ideal gas the internal energy U is only a function

of only T the partial derivative holding p constant becomes a total derivative

U

dU

=

= CV .

(14)

T p dT

Because we know that the general relationship between Cp and CV is given by

dU

dV

dQ

=

+p

.

Cp =

dT p

dT p

dT p

Which for an ideal gas and Eq. 14 becomes

RT

R

Cp = CV + p

= CV + p = CV + R .

T

p p

p

(15)

(16)

Which again is Fermi Eq. 33. For a monotonic gas with CV = 23 R the above gives

3

5

Cp = R + R = R

2

2

(17)

7

5

Cp = R + R = R .

2

2

From the definition of K =

Cp

CV

(18)

K =1+

R

CV

(19)

K =1+

R

3

R

2

=1+

5

2

=

3

3

(20)

=1+

7

2

= ,

5

5

(21)

K =1+

for its ratio of specific heats.

R

5

R

2

an Ideal Gas (Page 25-26)

For an adiabatic transformation dQ = 0 and from Eq. 9 we have

CV dT + pdV = 0 .

(22)

Inserting the ideal gas law pV = RT in the above for p gives a differential expression in terms

of only T and V . From this, the following sequence of manipulations (assuming constant

CV ) integrates this obtaining the following

RT

dV = 0

V

R dV

dT

+

= 0

T

CV V

R

log(T ) +

log(V ) = constant .

CV

CV dT +

TV

Defining K = 1 +

R

CV

R

CV

= constant .

(23)

(24)

(25)

(26)

T V K1 = constant .

(27)

For an initial temperature, volume configuration denoted by (T0 , V0 ) the above expression

becomes

T V K1 = T0 V0K1 .

(28)

For a diatomic gas we have K = 57 , so K 1 = 25 = 0.4. For an expansion that has its final

volume V twice its initial volume size 2V0 we have

T =

T0

K1

2

T0

0.75 T0 .

20.4

(29)

To derive the expression of an adiabatic expansion in terms of the variables p and V or p and

T we substitute the ideal gas law in Eq. 27 as follows. From ideal gas law we have pV = RT

or T = pV

when substitute into Eq. 27 gives

R

pV K1

V

= constant ,

R

(30)

pV K = constant .

(31)

or

This is Fermi Eq. 39 and is the equation between the variables p and V that must be true for

an adiabatic transformation of an ideal gas. In terms of p and T (replacing V with V = RT

p

in Eq. 27) it looks like

(RT )K1

= constant .

(32)

T

pK1

or

TK

= const.

(33)

pK1

which is equivalent to Fermi Eq. 40. Another way of obtaining the same expression can be

obtained by solving for V in Eq. 27 giving

V =

C

1

T K1

Here I will denote constants that dont need to be further specified by C. Putting this

expression for V into the ideal gas law (pV = RT ) gives

pC

= RT ,

T K1

(34)

K

p = C T 1+ K1 = C T K1 ,

(35)

A Comparison of the p-V Representations of Isothermal and Adiabatic Transformations (Page 26-27)

= VC for an isothermal transformation. From the previous

In the (V, p) diagram p = RT

V

section we see that an adiabatic transformation in the (V, p) diagram is governed by p = VCK ,

with K the ratio of specific heats. To explicitly determine the slope for each of these

transformations in the (V, p) plane we must evaluate the following derivatives

C1

dp

= 2

(36)

dV isotherm

V

and

C2

dp

= K+1

dV adiabatic V

(37)

We see that the adiabatic transformation will have a steeper slope when

C1

C2

> 2 .

K+1

V

V

(38)

In terms of V (assuming C1 C2 > 0 for simplicity) the above equation is equivalent to the

following sequence of algebraic transformations

1

V

K+1

<

V

V K+1 >

K +1 >

K >

K+1

1

V2

1

V2

V2

2

1.

>

(39)

(40)

(41)

(42)

(43)

Since this last equation is true for a general thermodynamical system, all previous manipulations are valid and we conclude that the slope of isothermal curve is steeper in general.

The weight of a constant density object in a gravitational field is given by the product of

the gravitational constant, the objects density, and the objects volume. For a fluid in a an

infinitesimal cylindrical slab of height dh and base area A this weight is given by

dW = gAdh .

To balance this weight, a pressure differential must exist between the top and bottom of the

fluid (which is maintained by the internal pressure) and is given by

dp =

dW

gAdh

=

= gdh .

A

A

(44)

We have explicitly introduced a minus sign in the pressure differential under the expectation

that the pressure should decrease dp < 0 as we move up in the atmosphere dh > 0. From

p

Eq. 44 can be written

the ideal gas law in terms of density = M

RT

dp =

gMp

dh

RT

(45)

To determine the molecular weight M of air we remember that since air is about 78%

Nitrogen, and 21% Oxygen so we can compute the molecular mass of air from its constitute

parts

MN2 = 2(14) = 28 g/mol

MO2 = 2(16) = 32 g/mol .

(46)

(47)

So the average molecular weight of air is given by an appropriately weighted linear combination of that for Nitrogen and Oxygen

Mair = 0.78(28) + 0.21(32) 28.56 g/mol .

(48)

A more accurate calculation gives Mair 28.97 g/mol. Fermi Eq. 40 can be written as

T p

K1

K

=C,

(49)

assuming the gas is expanding adiabatically. Taking the logarithm of both sides of this

equation we obtain

K1

log(T )

log(p) = log(C) .

(50)

K

Further taking the differential of both sides of the above equation gives

or solving for

dT

T

K 1 dp

dT

= 0,

T

K p

(51)

K 1 dp

dT

=

.

T

K p

(52)

gives

K 1 gM

dT

=

dh .

T

K

RT

(53)

This gives for the change in temperate with respect to height the following expression

dT

K 1 gM

=

,

dh

K

R

(54)

which is Fermi Eq. 42 in the book. Since air is mostly a diatomic gas we have that K = 57 .

Taking the remaining constants to be their standard CGS values of

g = 980 cm/s2

dyne cm

,

R = 8.314 107

mol K

we obtain

dT

= 9.8 105 deg/cm = 9.8 105 deg/kilometer .

dh

(55)

(56)

(57)

The expression

Ltotal = N L NL ,

is represented in two terms, the first N L , is the work done by the first engine and the

second NL is the work done by the heat. The total heat absorbed from T2 is given by

Q2,total = N Q2 NQ2 ,

while the total given up to temperature T1 , is

Q1,total = N Q1 NQ1 .

With the definitions given by Fermi Eq. 47 and Fermi Eq. 48 for (L and L) we have

Ltotal =

=

=

=

N L NL

N (Q2 Q1 ) N(Q2 Q1 )

N Q2 NQ2 N Q1 + NQ1

Q2,total Q1,total .

(58)

(59)

(60)

(61)

If Q2,total = 0, from the above equation we have that Ltotal = Q1,total which is Fermi Eq. 51.

Now as explained in the book Ltotal 0, and because of the equivalence between the magnitude of Ltotal and Q1,total we therefore must have Q1,total 0. Remembering the definition

of Q1,total and Fermi Eq. 49 the following manipulations derive the fact that the efficiency of

a reversible cyclic engine must be greater than that from a non-reversible cyclic engine.

Q1,total

N Q1

N

Q

N 1

Q2

Q

Q2 1

Q2 Q1

Q2

Q1

Q1

Q2

Q1

1

Q2

rev.

0

NQ1

(62)

(63)

Q1

(64)

Q1

(65)

Q1 Q2

Q2

Q1

Q1

Q2

Q1

1

Q2

nonrev.

(66)

(67)

(68)

(69)

(70)

We will step along each segment of the Carnot cycle, deriving expression that must be

satisfied due to the known nature of the transformation that occurs during the considered

segment. For instance, from the first law of thermodynamics we obtain that the transformation from A to B along an isothermal expansion must satisfy

UB UA + LAB = QAB Q2 .

(71)

For an isothermal expansion the work can be explicitly calculated and is found to be

LAB = RT2 log(

VB

)

VA

(72)

Since the assumed substance is an ideal gas where the internal energy is a function of only

temperature we have that UB = UA and thus

Q2 = LAB = RT2 log(

VB

)

VA

(73)

UC UD + LDC = QDC Q1

(74)

with (by the same reasoning UC = UD ) and the above simplifies as before

Q1 = LDC = RT1 log(

VD

)

VC

(75)

The two paths we have not considered are the two adiabatic ones CA and BD. On the CA

path the adiabatic constraint requires that

T1 VCK1 = T2 VAK1 ,

(76)

T2 VBK1 = T1 VDK1 .

(77)

Dividing these two expressions gives

VC

VD

K1

VA

VB

K1

(78)

VC

VA

=

.

VD

VB

(79)

Q2

T2

=

,

=

VD

Q1

T1

RT1 log( VC )

(80)

which expresses the ratio of heat extracted and emitted in terms of the two operating reservoir

temperatures.

From Fermi Eq. 43 we have L = Q2 Q1 which is equivalent to

1=

Q2

L

Q1 Q1

(81)

Using the relationship above to express the heat ratio in terms of the reservoir temperatures

we obtain

L

T2

(82)

1=

T1 Q1

Solving for Q1 gives

T1

,

T2 T1

which is Fermi Eq. 60. Now solving the above for L gives

T1 T2

T2

L=

Q1 = Q1

1 .

T1

T1

Q1 = L

(83)

(84)

Proof that the Total Entropy Must Increase under Heat Flow (Page

56)

The transfer of an amount Q between bodies A1 and A2 results in a decrease in entropy S1

for body A1 and an increase in entropy of S2 for body A2 . In terms of the heat transferred

at the lower temperature T1 and the higher temperature T2 we have

Q

T1

Q

= .

T2

S1 =

(85)

S2

(86)

S1 + S2 =

Q

Q(T2 T1 )

Q

=

> 0,

T1 T2

T1 T2

(87)

Since entropy is additive while probabilities are multiplicative our entropy function f must

satisfy the relation f (xy) = f (x) + f (y). Replaying y with 1 + this becomes

f (x(1 + )) = f (x) + f (1 + ) .

(88)

f (x) + xf (x) +

x2 2

f (1) 2

f (x) + O(3 ) = f (x) + f (1) + f (1) +

+ O(3 )

2

2

(89)

xf (x) + O(2 ) = f (1) + f (1) + O(2 ) .

(90)

Matching powers of epsilon on both sides we have f (1) = 0 and xf (x) = f (1) k or

f (x) =

k

x

(91)

Integrating, we obtain a functional form for the entropy of f (x) = k log(x) + constant.

The heat dQ received during an infinitesimal transformation is given by

U

U

dT +

+ p dV ,

dQ =

T V

V T

(92)

which is Fermi Eq. 79. Since for a reversible transformation dS = dQ

T

dQ

1

U

1 U

dS =

dT +

+ p dV

(93)

=

T

T T V

T

V T

For an ideal gas the heat received during an infinitesimal transformation of an ideal gas

comes in two parts as dQ = CV dT + pdV where p = RT

, giving

V

dQ = CV dT +

RT

dV

V

dS =

(94)

dQ

T

giving

CV

R

dT + dV .

T

V

(95)

Assuming that CV a constant (which is true for an ideal gas) we can integrate the above to

obtain

S = CV ln(T ) + R ln(V ) + a .

(96)

Which is Fermi Eq. 86. Since an idea gas has V =

of p and T obtaining

RT

p

RT

) + a.

p

(97)

S(p, T ) = CV ln(T ) + R ln(R) + R ln(T ) R ln(p) + a

(98)

= Cp ln(T ) R ln(p) + a + R ln(R)

(99)

or

which is Fermi Eq. 87. In the general case where the internal energy U is a function of both T

and V (and Cv is not constant), then Fermi Eq. 80 requires (since S is an exact differential)

and we can equate mixed partials

1 U

1

U

=

+p

.

(100)

V T T V

T T

V T

evaluating the derivatives of both sides we obtain

2

1 2U

1

U

1

p

U

.

=

+p

2 +

+

T V T

V

T

T T V

T

Which upon canceling the second derivative term from both sides gives

U

p

+p=T

V

T V

or

U

V

=T

p

T

(101)

(102)

(103)

which is Fermi Eq. 88 in the book. Note that all the derivations up to this point have been

independent of the equation of state. If in fact we further specify that our operating medium

is an ideal gas with an equation of state given by the ideal gas law

p=

RT

V

we can evaluate our general expression equation 103. For the ideal gas law this gives

R RT

U

=T

= 0.

(104)

V T

V

V

From which we can conclude that U does not depend on T .

Choosing (T, p) as the independent state variables Fermi Eq. 23 gives for dQ

!

U

V

V

U

+p

dT +

+p

dp

dQ =

T p

T p

p T

p T

(105)

(for a general path dS dQ

) and the above

T

T

becomes

!

U

V

1

U

V

1

+p

dT +

+p

dp

(106)

dS =

T

T p

T p

T

p T

p T

Again since dS must be a perfect differential equating the cross derivatives we have

!

U

V

U

V

1

1

+p

=

+p

.

p T

T p

T p

T T

p T

p T

(107)

constant to T and vice versa) gives

2

V

U

U

1

V

2V

1

=

+p

2

+

+p

(108)

T pT

T

T p

p T

p T

T

2

1

U

2V

+

(109)

+p

T pT

T p

or when one cancels common terms, one obtains

V

V

U

= p

T

p T

p T

T p

which is Fermi Eq. 89 in the book.

(110)

With p and V as independent variables with Fermi Eq. 24 dQ can be expressed as

"

#

U

U

dp +

+ p dV = dQ .

p V

V p

dQ

T

"

#

1

U

1 U

dQ

dp +

+ p dV .

=

dS =

T

T p V

T

V p

On a reversible path dS =

(111)

(112)

As in all previous derivations, using the knowledge that dS is a perfect differential we can

equate mixed partials of S obtaining

1 U

1 U

=

+p

(113)

V T p

p T V

which upon expanding the above gives us

2

1 U

1

U

U

1 2U

1

+

=

+p +

+1

V T p

T pV

p T

V

T pV

or

1

2

T

T

V

p

U

p

1

= 2

T

T

V

U

V

+p

1

.

T

(114)

(115)

T

T =

V

p

U

p

+

V

T

p

U

V

+p

(116)

With the change in volume dV and dU given by

dV = (v2 (T ) v1 (T ))dm

dU = (u2 (T ) u1 (T ))dm

(117)

(118)

where vi and ui are the specific volume and specific internal energy of the substance. The

direct ratio with

u2 u1 + p(v2 v1 ) =

gives

dU

dV

=

T

u2 (T ) u1 (T )

p(v2 (T ) v1 (T ))

=

=

p

v2 (T ) v1 (T )

v2 (T ) v1 (T )

v2 v1

(119)

U

p

=T

p

V T

T T

we have by inspection that

T

dp

=

.

dT

v2 v1

(120)

(121)

Now with the given value of

= 540cal/gm = 540(4.185 107erg)/gm = 2259 107erg/gm

and since water boils at 100 Centigrade, T = 100 + 273.15 = 373.15K, so that the Clapeyron

equation gives

(2259 107erg/gm)

dp

=

= 3.61 104erg/cm3 K

3

dT

(373.15K)(1677 1.043)cm /gm

Remembering the conversion that

1

dyne

= 7.5 105cm Hg

2

cm

we have then

dp

cm Hg

= 2.7

.

dT

K

Normally for gas-liquid or a gas-solid interface

v1 v2

(122)

(123)

Here v1 is the specific volume of the liquid/solid and v2 is the specific volume of gas. Fermi

Eq. 6 (the equation of state for an ideal gas) gives

p

V

1

=

RT .

m

M

(124)

V

is the specific volume or the volume per gram so, since index 2 corresponds

The expression m

RT

to the gas we have v2 = M

, so that the Clapeyron equation becomes

p

Mp

dp

= =

=

RT

dT

T v2

RT 2

T M

p

(125)

For water vapor over its liquid at the boiling temperature we get (remembering that M =

18gm/mol)

(2260 107erg/gm)(18gm/mol)(1atm)

dp

=

.

(126)

dT

(8.314 J/molK)(373.1K)2

Remembering the unit conversion that 1erg = 107 J and 1atm = 1.01 105 Pa, the above

becomes

dp

(2260J/gm)(18gm/mol)(1.01 105 Pa)

3

4 dynes

=

=

3.55

10

Pa/K

=

3.55

10

.

dT

(8.314 J/molK)(373.1K)2

cm2 K

(127)

In equation 125, if the heat of vaporization can be assumed independent of temperature

then this expression can be integrated giving

M

p = Ce RT

(128)

As an example of a solid-liquid system consider melting of ice then we are told that

= 80cal/cm = 80 4.185 107erg/gm = 334.8 107erg/gm .

(129)

335 107erg/gm

dp

=

=

= 1.35 108 erg/cm3 K

3

dT

T (v2 v1 )

(273.1K)(1.00013 1.0907)cm /gm

Remembering that

1

(130)

dyne

= 9.86 107atm

cm2

dp

= 1.33 102 atm/K = 133 atm/K

(131)

dT

This increases in pressure by 134 atmospheres lowers the melting point by 1 Kelvin. The

more pressure ice is under the easier it is to melt it.

The Van der Waals Critical State in terms of the constants a and b

(Page 72-73)

A gas that satisfies the Van der Waal equation of state must satisfy

a

p + 2 (V b) = RT .

V

(132)

(V 2 p + a)(V b) = V 2 RT

V 3 p bV 2 p + aV ab = V 2 RT

pV 3 + (bp RT )V 2 + aV ab = 0 .

(133)

(134)

(135)

Given T and p, to obtain a cubic equation in V we multiplying both sides of the above by

V 2 and expanding the product on the left hand side producing

pc V 3 (bpc + RTc )V 2 + aV ab = 0 .

(136)

Because the pressure and temperature are evaluated at the critical isotherm, this expression

must have Vc as a root of third order. Mathematically this means that the above should be

represented as pc (V Vc )3 = 0 for some choice of Vc . Expanding this cube we have

pc V 3 3pc V 2 Vc + 3pc V Vc2 pc Vc3 = 0 .

(137)

3pc Vc = (bpc + RTc )

3Vc2 pc = a

pc Vc3 = ab

(138)

(139)

(140)

This is a set of three equations involving three unknowns of (Vc , pc , Tc ). Solving for Vc using

the second and third equation above by dividing the third equation by the second gives

Vc = 3b .

(141)

Inserting this equation into the second equation from 138 we see that pc is given by

pc =

a

a

.

=

2

3Vc

27b2

(142)

a

a

3(3b)( 27b

3Vc pc bpc

2 ) b( 27b2 )

Tc =

=

=

R

R

a

b

1

3

1

27

8 a

27 Rb

(143)

which is Fermi Eq. 100. As suggested in the text introducing the non-dimensional variables

p

pc

V

=

Vc

T

=

Tc

P =

(144)

(145)

(146)

p = Ppc

V = V Vc

T = T Tc ,

into the Van der Waals equation of state (Fermi Eq. 99)

a

p + 2 (V b) = RT ,

V

(147)

(148)

(149)

(150)

the following

Ppc +

a

2

Vc V 2

(Vc V b) = RT Tc ,

(151)

or

a

P+

pc Vc2 V 2

RTc

b

=

T .

V

Vc

V c pc

(152)

Now the factors involving our recently determined critical constants simplify as follows

a

1

a

= 1 =3

=

a

2

9b

pc V c

27b2

3

b

b

1

=

=

Vc

3b

3

8 a

R 27 Rb

8

RTc

=

=

a

V c pc

3b 27b2

3

and we get for equation 152

3

8

1

P+ 2

= T

V

V

3

3

(153)

Expressions for internal energy and entropy in a Van der Waals gas

(Page 73-75)

Using the Van der Waals equation of state expression (Fermi Eq. 99) by solving for the

pressure we obtain

RT

a

.

(154)

p= 2+

V

V b

Now for any thermodynamic system the internal energy change with respect to volume is

given by (holding temperature constant)

U

p

=T

p.

(155)

V T

T V

Evaluating this expression for the p = p(V ) relation given by the Van der Waals equation of

state we obtain

U

R

a

RT

a

=T

+ 2

= 2.

(156)

V T

V b

V

V b

V

Integrating this expression (with respect to V ) gives

U =

a

+ f (T ) ,

V

(157)

where f (T ) is an arbitrary function of temperature. This is Fermi Eq. 103. To derive the

entropy of a Van der Waals gas we first evaluate the specific heat at constant volume given

by

U

Q

=

= f (T ) ,

(158)

CV =

T V

T V

f (T ) = CV T + w .

This expression when put back into the expression for the internal energy U results in

a

U = + CV T + w .

(159)

V

Now to evaluate the entropy we can perform the following manipulations exactly as in the

book

dQ

dS =

T

1

(dU + pdV )

=

T

1

a

a

1

RT

=

2+

dV

(CV dT + 2 dV ) +

T

V

T

V

V b

a

a

R

dT

+

dV

dV +

dV

= CV

2

2

T

TV

TV

V b

dT

R

= CV

+

dT ,

(160)

T

V b

which when integrated with respect to T gives

S = CV ln(T ) + R ln(V b) + constant .

(161)

Which is Fermi Eq. 105. Compare this expression with Fermi Eq. 86 the similar expression

for an ideal gas which is

S = CV ln(T ) + R ln(V ) + a

Now along an adiabatic transformation by definition dQ = 0, equivalently dS = 0, or

S = constant and the above expression can be manipulated as follows

CV ln(T ) + R ln(V b) = C1

R

ln(V b) = C2

ln(T ) +

CV

T (V b)R/CV = C3

(162)

where C1 , C2 , and C3 are all constants. This expression can be recognized as Fermi Eq. 106.

The derivation given in the book proceeds smoothly until about the middle of the page

where the statement dF (A)/dT = S(A) is made. This expression can be derived as

follows. Considering the definition of the free energy F (A) as F = U T S we have that the

temperature derivative of F given by

dF (A)

dU(A)

dS(A)

=

T

S(A)

dT

dT

dT

1

(dU(A) T dS(A)) S(A)

=

dT

= S(A)

where we have used the fact that from the first and second law of thermodynamics dU =

dQ dW = T dS dW or dU T dS = dW = 0 if no work is done.

Since S(A) = (U F )/T from the definition of the free energy the temperature derivative

above can be written in terms of the free energy and internal energy as

dF (A)

F (A) U(A)

=

.

dT

T

T

To relate this to the derivative of work with respect to temperature and derive the isochore

of Vant Hoff recall Fermi Eq. 115 or

dL

dF (A) dF (B)

=

,

dT

dT

dT

we can use the expression above to replace the derivatives of the free energy with respect to

temperature with expressions involving the free energy itself as

dF (A) dF (B)

F (A) U(A) F (B) U(B)

dL

=

.

dT

dT

dT

T

T

multiplying both sides by T we obtain

T

dL

= F (A) U(A) (F (B) U(B)) = F (A) F (B) (U(A) U(B)) = L + U

dT

where we have used Fermi Eq. 114 of L = F (A) F (B). Thus in summary we have derived

U = L T

dL

dT

(163)

WWX: I have not finished this section ... start

WWX: page 2 of the second set of scanned notes

From Fermi Eq. 112 we have L F

pdV =

so

p =

F

V

(164)

(165)

F = Cv T + W (Cv T + R log(V ) + a)T

= Cv T + W T (Cp log(T ) R log(p) + a + R log(R))

(166)

(167)

(Page 82-83)

L F gives pV (B) pV (A) F (A) F (B). Now defining

= F + pV = U T S + pV

(168)

(169)

giving (B) (A). From the book: To find an equilibrium state for a system that has

pressure and temperature we look for the minimum of the Gibbs Free energy . For a general

system, find what ... thermodynamic potential be it F U T S, = U T S + pV now

since = U T S + pV we have that

U

S

V

=

T

+V +p

(170)

p T

p T

p T

p T

since dQ = T dS = dU + pdV ,

T

S

p

=

T

U

p

(171)

U

U

V

V

=

p

+V +p

=V

p T

p T

p T

p T

p T

which is Fermi Eq. 123. In the same way

U

S

V

=

ST

+p

T p

T p

T p

T p

T dS = dU + pdV

so that

T

S

T

U

T

+p

(172)

(173)

(174)

V

T

(175)

U

U

V

V

=

S

p

+ p

T p

T p

T p

T p

T p

(176)

= U T S + pV . Now T is the same for both vapor and liquid phases and P is the same

for both vapor and the liquid at least at the surface or in zero gravity? Now = 1 + 2 ,

i.e. on the space shuttle or with very little liquid. pV = RT and

= m1 1 (T ) + m2 2 (T )

(177)

= (m1 + dm1 )1 (T ) + (m2 dm1 )2 (T ) = + dm1 (1 2 )

(178)

As was at a minimum. In order that the value of not change from that of , we must

have 1 = 2 , which is

U1 T S1 + pV1 = U2 T S2 + pV2

(179)

or

U2 U1 T (S2 S1 ) + p(V2 V1 ) = 0

(180)

d

d

dp

d

(U2 U1 ) (S2 S1 ) T

(S2 S1 ) +

(V2 V1 ) + p (V2 V1 ) = 0

dT

dT

dT

dT

dU

dv

ds

=

+p

dT

dT

dT

dU

dS

dV

T

+p

=0

dT

dT

dT

dp

(V2 V1 ) = 0

(S2 S1 ) +

dT

(183)

dp

=

dT

T (V2 V1 )

(185)

with S2 S1 = T , we obtain

=

=

=

=

(181)

U T S + pV

cV T + W T (Cp log(T ) R log(p) + a + R log(R)) + pV

cV T + W + pV T (Cp log(T ) R log(p) + a + R log(R))

cV T + W + RT T (Cp log(T ) R log(p) + a + R log(R))

(182)

(184)

(186)

(187)

(188)

(189)

= Cp T + W T (Cp log(T ) R log(p) + a + R log(R))

dF (A)

dU

dS

=

T

S(A)

dT

dT

dT

1

(dU T dS) S(A)

=

dT

= S(A)

(190)

(191)

(192)

(193)

dU = dQ dW = T dS dW

(194)

F (A) U(A)

dF (A)

=

dT

T

T

(195)

since F = U ST , we have that S = F U

T

and

dF (A) dF (B)

dL

=

(196)

dT

dT

dT

then

dL

dF (A)

dF (B)

T

=T

T

(197)

dT

dT

dT

each term in the above can be replaced as

T

dL

= F (A) U(A) (F (B) U(B)) = F (A) F (B) (U(A) U(B)) = L + U (198)

dT

so we have

T

dL

= L + U

dT

(199)

giving

dL

dT

which is Fermi Eq. 117. From Fermi Eq. 112 we have L F

F

pdV =

V T

U = L T

so

p =

F

V

(200)

(201)

(202)

F = Cv T + W (Cv T + R log(V ) + a)T

= Cv T + W T (Cp log(T ) R log(p) + a + R log(R))

(203)

(204)

= F + pV = U T S + pV

(205)

(206)

giving (B) (A). From the book: To find an equilibrium state for a system that has

pressure and temperature we look for the minimum of the Gibbs Free energy . For a general

system, find what ... thermodynamic potential be it F U T S, = U T S + pV now

since = U T S + pV we have that

U

S

V

=

T

+V +p

(207)

p T

p T

p T

p T

since dQ = T dS = dU + pdV ,

T

S

p

=

T

U

p

(208)

U

U

V

V

=

p

+V +p

=V

p T

p T

p T

p T

p T

which is Fermi Eq. 123. In the same way

U

S

V

=

ST

+p

T p

T p

T p

T p

T dS = dU + pdV

so that

U

V

S

=

+p

T

T p

T T

T p

U

U

V

V

=

S

p

+p

T p

T p

T p

T p

T p

(209)

(210)

(211)

(212)

(213)

= U T S + pV . Now T is the same for both vapor and liquid phases and P is the same

for both vapor and the liquid at least at the surface or in zero gravity? Now = 1 + 2 ,

i.e. on the space shuttle or with very little liquid. pV = RT and

= m1 1 (T ) + m2 2 (T )

(214)

= (m1 + dm1 )1 (T ) + (m2 dm1 )2 (T ) = + dm1 (1 2 )

(215)

As was at a minimum. In order that the value of not change from that of , we must

have 1 = 2 , which is

U1 T S1 + pV1 = U2 T S2 + pV2

(216)

or

U2 U1 T (S2 S1 ) + p(V2 V1 ) = 0

(217)

d

d

dp

d

(U2 U1 ) (S2 S1 ) T

(S2 S1 ) +

(V2 V1 ) + p (V2 V1 ) = 0

dT

dT

dT

dT

ds

dU

dv

=

+p

dT

dT

dT

dS

dV

dU

T

+p

=0

dT

dT

dT

dp

(S2 S1 ) +

(V2 V1 ) = 0

dT

(220)

dp

=

dT

T (V2 V1 )

(222)

with S2 S1 = T , we obtain

(218)

(219)

(221)

=

=

=

=

U T S + pV

cV T + W T (Cp log(T ) R log(p) + a + R log(R)) + pV

cV T + W + pV T (Cp log(T ) R log(p) + a + R log(R))

cV T + W + RT T (Cp log(T ) R log(p) + a + R log(R))

(223)

(224)

(225)

(226)

= Cp T + W T (Cp log(T ) R log(p) + a + R log(R))

(227)

(228)

(229)

k = mi,k m

(230)

mj,k = mj,k + m

(231)

= i + j

j

i

(m) +

m

=

mi,k

mj,k

i

j

m

m = 0

=

mj,k

mi,k

(232)

j

i

=

mj,k

mi,k

(233)

(234)

(235)

How many equations like this do we have? f phases and n components, since each component

n of them in a given phase i can go to any of the other f 1 phase (nothing happens if it

goes to itself. We have n(f 1) equations for equilibrium. Each

depends only on ratios

i

of the mk,i . The number of ratios there are like this are n 1. Then for all

is f (n 1)

with T and p we have f (n 1) + 2 variables. Let v be the number of unknowns minus the

number of equation. Then

v = (n 1)f + 2 n(f 1)

= 2+nf

(236)

(237)

v = 2+11 =2

(238)

v = 2+21 =3

(239)

Now example #3 is 2 phases solid and liquid has f = 2 and one component so n = 1 so we

have

v =2+nf =2+12= 1

(240)

v =2+nf =2+13= 0

(241)

we have L = ev. Power exerted by DC current is given by P = V I with V the voltage and

I the current. Now current is charge per unit time. Thus the work is voltage times charge.

U(T, e) = U(T ) eU(T )

(242)

U = eU(T )

(243)

dL

= U

(244)

dT

d(eV )

eV T

= eU

(245)

dT

dv

=u

(246)

vT

dT

which is Fermi Eq. 134. e = Cv(T ) and dL = 12 dCV 2 (T ) energy of an isolated capacitor is

given by

1 e2

(247)

2C

1 e2

1 e2

)=

dC

(248)

dL = d(

2C

2 C2

LT

But e = Cv and dL =

1 C 2 v2

dC

2 C2

= 21 v 2 dC

(249)

1

1

dQ = dU + dL = d(U(T ) CV (T )u(T ) + Cv 2 (T )) + dCv 2

2

2

dU

dv

dU

dv

= dT

C u Cv

+ Cv

dT

dT

dT

dT

1

1

+ dC vu + v 2 + v 2

2

2

dQ

dT dU

du

dv

dv

dS =

=

Cv

Cu

+ Cv

T

T

dT

dT

dT

dT

dC 2

+

v vu

T

"

dU

dT

CV

1

T

dU

dT

dv

Cu dT

+ CV

T

dV

dT

=

T

dU

dV

dv

v

u

+v

dT

dT

dT

v 2 vu

T

(250)

(251)

(252)

(253)

(254)

(255)

(256)

v 2 vu 2vv v u vu

+

T2

T

(257)

which gives

v du

u dv

v dv

2v dv

u dv

v du

v2

vu

+

=

2+ 2

T dT

T dT

T dT

T dT

T dT

T dT

T

T

vu

v dv

v2

2 =

2

T

T

T dT

v

u

dv

=

T

T

dT

which gives

vT

dv

=u

dT

(258)

(259)

(260)

(261)

End page 10 of second set of scanned notes

begin page 13 of second set of scanned notes

In Fermi Eq. 136 if k(T ) 1 then

[A1 ]n1 [A2 ]n2 [Ar ]nr = k(T )[1 ]m1 [2 ]m2 [s ]ms

(262)

Generally we have that [A1 ]n1 [A2 ]n2 [Ar ]nr 1, so the reaction is shifted to the right.

Now the definition of [A] is the number of moles of A divided by the volume. So [A]M is

the mass of A divided by the volume.

LI = RT

n

X

ni

(263)

i=1

p1 V1 = n1 RT

(264)

concentration. To insure that we get m1 moles in the first cylinder which we can extend to

+ we must require that

m1

V1 [1 ] = m1 V1 =

(265)

[1 ]

where [1 ] concentration of elements 1 .

L = LI + LII

!

n

s

X

X

ni = F

= RT

mj

j=1

(266)

(267)

i=1

1

) + a1 }

[A]

= n1 {Cv1 T + w1 T (Cv1 log(T ) R log([A]) + a1 }

(268)

(269)

(270)

r

X

FI =

(271)

(272)

i=1

FF =

s

X

j=1

FI FF = L becomes

!

s

n

n

s

X

X

X

X

RT

mj

ni =

ni {Cvi T +wi T (Cvi log(T )R log([Ai ])+ai }

mj {Cvi T +wi T (Cvi log(T )

i=1

j=1

i=1

j=1

(273)

RT

s

X

mj

j=1

r

X

i=1

ni

r

X

i=1

s

X

mj Cv j T +mj wj m

ni Cvi T +ni wi ni T Cvi log(T )+ni RT log([Ai ])+ni ai T

j=1

(274)

dividing by RT we have

s

X

mj

j=1

r

X

ni =

i=1

r

X

ni Cv

i=1

s

X

mj Cv j

j=1

ni wi ni Cvi log(T )

ni ai

+ ni log([Ai ]) +

RT

R

R

(275)

mj Cv j log(T )

mj wj

mj aj

+ mj log([Bj ]) +

(276)

RT

R

R

so we have that

r

X

ni log([Ai ])

i=1

s

X

mj log([Bj ]) =

j=1

r

X

ni Cv

i=1

RT

s

X

mj Cv j

j=1

ni wi ni Cvi log(T ) ni ai

+

+ n(277)

i

RT

R

R

mj Cv j log(T ) mj aj

mj wj

+

+

+(278)

mj

RT

R

R

which gives

[A1 ]n1 [A2 ]n2 [Ar ]nr

log(

[B1 ]m1 [B2 ]m2 [Br ]mr

r

s

X

ni Cvi log(T ) X mj Cvj log(T )

=

R

R

i=1

j=1

r

X

ni wi

i=1

j=1

RT

mj aj

+ mj

R

j=1

r

X

ni Cv

i=1

s

X

mj Cv j

RT

RT

s

X

mj wj

RT

ni ai

+ ni

R

(279)

(280)

(281)

(282)

T

log( ) = log(

r

X

i=1

or

log( ) = log(T

n1 Cv1

R

m1 Cv1

R

T

T

n2 Cv2

R

m2 Cv2

R

n3 Cv3

R

nr Cvr

R

m3 Cv3

R

ms Cvs

R

r

X

i=1

X

mj wj

ni wi

log(exp(

)) +

log(exp(

))

RT

RT

j=1

(283)

s

X

mj Cv j

mi aj

ni Cvi ni ai

log(exp(

+

+ ni )) +

log(exp(

+

+ mj ))

R

R

R

R

j=1

1

R

Pr

1

i=1 ni Cvi R

Ps

j=1 mj Cvj

1

[A1 ]n1 [A2 ]n2 [Ar ]nr

= exp(

m

m

m

s

1

2

[B1 ] [B2 ] [Bs ]

R

which is times

T

P

P

mj Cv

mj a

mj w

exp( sj=1 R j + R j + mj )

exp( sj=1 RT j )

P

)+log(

)

)+log(

P ni Cvi ni ai

i wi

)

exp( ri=1 nRT

+ R + ni )

exp( ri=1 RT

(285)

( s

X

mj (R +

Cv j

r

X

+ aj )

j=1

1

R

(284)

P

r

ni (R + Cvi + ai ) ) (286)

i=1

i=1

ni Cvi

Ps

j=1

mj Cv j

(287)

1

exp(

RT

r

X

i=1

ni wi

s

X

mj wj

j=1

(288)

Since F = U T S and = U T S + pV the Free energy is given by

pi =

RT

V

ni

Cv1 T +W1 T (Cv1 log(T )R log([A1 ])+a1 )+V [A1 ](Cv1 T +W1 T (Cv1 log(T )R log([A1 ])+a1 ))

(289)

so

F =V

r

X

i=1

s

X

j=1

(290)

F

F

F

F

F

F

F

F

n1

n2

n3 . . .

nr ++

m1 +

m2 +

m3 +. . .+

ms

[A1 ]

[A2 ]

[A3 ]

[Ar ]

[B1 ]

[B2 ]

[B3 ]

[Bs ]

(291)

which gives

F =

F

F

F

F

F

F

F

F

[A1 ]

[A2 ]

[A3 ]. . .

[Ar ]++

[B1 ]+

[B2 ]+

[B3 ]+. . .+

[Bs ] = 0

[A1 ]

[A2 ]

[A3 ]

[Ar ]

[B1 ]

[B2 ]

[B3 ]

[Bs ]

(292)

From Fermi Eq. 140. we have

r

r

X

X

TR

F

=V

(Cvi + Wi T (Cvi log(T ) R log([Ai ]) + ai ) + V

[Ai ]

= V T R (293)

[Ai ]

[Ai ]

i=1

i=1

This is incorrect. You are taking the derivative of the concentration [Ai ] not the summation

variable [Ai ]. The above is taking the derivative of the summation variable index [Ai ] we get

RT

F

= V {Cvi T + wi T (Cvi log(T ) R log([Ai ]) + ai }+V [Ai ]

= V {Cvi T + wi T (Cvi log(T ) R lo

[Ai ]

[Ai ]

(294)

In the same way

F

(295)

[Bi ]

Then

F = [A1 ]V (Cv1 T +w1 T (Cv1 log(T )R log([Ai ])+ai )+RT )[A2 ]V (Cv2 T +w2 T (Cv2 log(T )R log([Ai ])

(296)

or

r

X

i=1

s

X

j=1

U =

s

X

mj (Cv j T + wj )

j=1

H = U =

r

X

n

mj Cv j T + wj T (Cv j log(T ) R log(

(297)

ni (Cvi T + wi )

(298)

i=1

r

X

ni (Cvi T + wi )

s

X

wj (Cv j T + wj )

(299)

j=1

i=1

r

X

d log(k(T ))

1

=

dT

TR

Cvi ni

i=1

s

X

j=1

Cv j mj

1

RT 2

(300)

C3

k(T ) = C1 T C2 e RT

(301)

so that

log(k(T )) = log(C1 ) + C2 log(T )

C3

C3

log(e) = log(C1 ) + C2 log(T )

RT

RT

(302)

so that

1

RT

r

X

i=1

Cvi ni

s

X

j=1

Cv j mj

1

RT 2

d log(k(T )

C2

C3

=

+

dT !

T

RT 2

r

s

X

X

ni wi

mj wj

i=1

j=1

=

=

1

RT 2

H

RT 2

r

X

i=1

T Cvi ni + ni wi

s

X

j=1

T Cv j m

Note that H = H(T ) thus we can see the temperature dependence. If n1 + n2 + . . . + nr <

m1 + m2 + . . . ms , then shifting the equation to the right increases the pressure.

[A1 ]n1 [A2 ]n2 [Ar ]nr

= k(T )

[B1 ]n1 [B2 ]n2 [Bs ]ns

(307)

Compress the system shrinking V causes the concentrations [A] and [B] to increase. Because

of the concentration inequality n1 + n2 + . . . + nr < m1 + m2 + . . . ms the left hand side

decreases to prevent this [A] increases by the [B] stays the same which implies that the

reaction shifts towards the reactants.

Problem 1

2A A which gives

[A]2

= k(T )

[A2 ]

(308)

is the equation of the law of mass action. Here [A] is in units of number of moles per the

volume and we are told that our reaction constant k is given by k(18C) = 1.7 104. Daltons

law of partial pressure says that p = 1 atm = pA + pA2 with pA the partial pressure of the A

species and pA2 the partial pressure of the A2 species. Then we have that

pA =

nA RT

= [A]RT

V

(309)

and

pA2 = [A2 ]RT

(310)

(311)

so

so [A]2 = k(T )[A2 ] which when put in above we have

p = ([A] +

or

[A]2

)RT

k(T )

(312)

p

[A]2

+ [A]

=0

k(T )

RT

(313)

1.01 105 Pa

41.72J//m3

p

=

=

= 41.72mol/m3

RT

(8.314J/molK)(273.15 + 18K)

J/mol

so we have for [A] the following

q

1

1 1 4 k(T

)

[A] =

1

2 k(T

)

P

RT

1

=

1+

2

k(T )

4p

k(T )RT

= 8.413 102mol/V

(314)

(315)

[A2 ] =

RT

[A] = 41.72 8.413 102 = 41.64 mol/m3

p

(316)

[A]2

= 1.6997 104

[A2 ]

(317)

since we are asked for the percentage of A we remember that nA = [A]V and nA2 = [A2 ]V

[A]

A

= [A]V[A]V

= [A]+[A

= 2.01 103 = 0.201

so the percentage of A is given by = nAn+n

+[A2 ]V

2]

A

2

Problem 2

We have H = 50000cal/mol degree of dissociation a H > 0 which means that this is an

exerthermal reaction expect raising the temperature to shift the reaction towards the left

and we should have an increase in the concentration of A. If I write the equation for the

[A]2

chemical reaction in the other order, I would flip the concentration ratio [A

but would not

2]

change the term eH/RT which would give a different equation. Where is the inconsistency.

Would be then than H should be given as the heat of reaction from the left to right. Which

if we switch the order of the chemical equation we switch the sign of H.

d log(k(T ))

H

=

dT

RT 2

so

log(k(T )) = C1

so that

H

RT

k(T ) = C2 e RT

therefore we have

H

[A]2

= C2 e RT = k(T )

[A2 ]

(318)

(319)

(320)

(321)

RT = (8.314 J/molK)(291.15K) = 2.42 103J/mol

since we know that 1J = 0.2388cal we have that RT = 5.78 103cal/mol, so that

H

50000cal/mol

=

= 8.64 101

RT

5.78 103cal/mol

(322)

(323)

which gives C2 = exp(8.64 101) 1.7 104 = 5.66 1033, which is huge. Therefore k(T = 18 C) =

H

) = 2.07 104. Now to find the percentage of A we remember that p =

5.66 1033 exp( RT

pA + pA2 = [A]RT + [A2 ]RT

[A] + [A2 ] =

P

RT

(324)

[A] +

p

[A]2

p

[A]2

=

+ [A]

=0

k(T )

RT

k(T )

RT

(325)

[A] =

1

k(T )

14

1

2 k(T

)

P

RT

(326)

[A]2

[A2 ] = 4.14 101 < 4.16 101

[A2 ] =

k(T )

(327)

so the percentage A is given by 2.22 103 or 0.22 percent which has increased the concentration of A as expected.

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Problem Solutions

Chapter 1 (Thermodynamic Systems)

Problem 1

Since the gas is expanding against a constant atmosphere (at pressure p) the total work L

done by the gas can be written as

Z V2

pdV = p(V2 V1 )

(328)

L=

V1

L = 2.34 atm (4.01 3.12) liters = 2.082 atm liters

(329)

To convert this result into CGS units (centimeters, grams, and seconds) we remember that

1 atm = 1.01 105 Pa = 1.01 105

1 liter = 103 m3

1 N = 105 dyne

1 m = 100 cm

N

m2

(330)

(331)

(332)

(333)

Thus we have

N

103 m3

m2

= 1.01 102N m

= 1.01 102 105 dyne 102 cm

= 1.01 109dyne cm .

(334)

(335)

(336)

(337)

L = 2.103 102N m = 210.3 N m = 2.103 109dyne cm

(338)

Problem 2

Since we are told that the gas is hydrogen (H2 ), looking to the periodic table gives us that

hydrogens mass per unit mole (molecular weight) is given by M = 2g/mole. The rest of the

problem provides the gass mass m, volume V , and temperature T as

m = 30 g

T = 18 C = 18 + 273.15 = 291.15 K

V = 1 m3

(339)

(340)

(341)

pV =

m

RT

M

gives

p=

m

1

30g

J

1

J

RT

=

8.314

291.15 K

= 3.63 104 3

3

M

V

2g/mole

mole K

1m

m

(342)

p = 3.64 104

N

= 3.64 104 Pa .

m2

(343)

1 Pa =

1

atm = 9.9 106 atm .

1.01 105

p = 3.59 101atm .

(344)

Nitrogen exists as a diatomic molecule (N2 ) under standard conditions and thus has a molecular weight of

M = 2 14 grams/mole = 28 grams/mole .

The idea gas law gives for the density

Mp

m

=

.

(345)

V

RT

In the problem, we are assuming that the Nitrogen is at 0 Celsius or 273.15 K. As such, the

density will be completely determined once we have specified a pressure. Since none is given

in this problem we will assume that atmospheric conditions apply and that the pressure is

1 atm = 1.01 105 Pa. With this assumptions the density is given by

=

=

=

Since the specific volume is

that

(8.314 J/mole K) (273.15 K)

(103 kg)(kg/ms2 )

grams Pa

= 1244

1244

J

kg m2 /s2

kg

g

1.244 3 = 1.244 103 3 .

m

cm

defined to be the reciprocal of the density, we have numerically

v=

m3

cm3

1

= 0.8038585

= 803.8585

.

kg

g

(346)

Problem 4

From Fermi Eq. 9 in the book we have the work for an isothermal expansion is given by

L=

m

V2

m

p1

RT log( ) =

RT log( ) .

M

V1

M

p2

(347)

m

M

R

T

p1

p2

=

=

=

=

=

=

10 g

32.0 g/mol

8.314J/molK

20 C = 293.15 K

1 atm

0.3 atm

10g

J

1

L=

8.314

(293.15 K) log( )

32g/mol

molK

0.3

(348)

which simplify to

L = 916.9J .

(349)

Problem 1

From the first law of thermodynamics in canonical form (dU = dQ dW ) and the energy

unit conversion between cals and ergs of

1cal = 4.185 107erg ,

we obtain

dW = 3.4 108 erg

dQ = 32 cal = 32(4.185 107 erg) = 1.339 109 erg .

(350)

(351)

dU = 1.339 109 3.4 108 = 9.9 108 erg = 23.8 cal

(352)

Problem 2

The work done by an isothermal expansion is given by Fermi Eq. 9

m

p1

V2

m

=

.

RT log

RT log

L=

M

p2

M

V1

(353)

m

Since M

is the number of moles of the gas under consideration for the specifics for this

problem we have that

5

L = (3mol)(8.314 J/molK)(0 + 273.15 K) log

= 3.48 103J = 831.54 cal .

3

Since we are considering an ideal gas whos internal energy is a function of temperature only

the first law of thermodynamics dU = dQ dW simplifies since the expansion considered is

isothermal (dU = 0) to give

dQ = dW .

Because of this relationship, we have that the number of calories absorbed, or Q, is given by

Q = W = L which is computed above.

For this problem we desire to compute the amount of work performed by the gas when it

undergoes a straight line transformation between (V0 , p0 ) and (V1 , p1 ) in the (V, p) plane. In

the specific case given in this problem the initial and final volumes (and temperatures) are

specified while the initial and final pressures must be computed from the equation of state

for an ideal gas. Using the ideal gas law to derive the corresponding pressure p0 we have

p0 =

= 1.15 105Pa .

2

3

2.1 10 m

p1 = 1.99 105Pa .

Since we have not derived an expression for the work done under a straight line transformation in the (V, p) plane we do so now and then use its result to evaluate this problem. The

work a gas performs under any transformation in the (V, p) plane is given by

Z

Z

W = L = p dV = p(V ) dV .

Where we have expressed the path in the (V, p) plane as a function of V explicitly with the

notation p(V ). When the path in the (V, p) plane is a line connecting the state (V0 , p0 ) to

(V1 , p1 ) can derive and explicit formula for the path by equating the slope at any point on

the line to the slope between the two end points as

p1 p0

p(V ) p0

=

.

V V0

V1 V0

On solving for p = p(V ) we obtain

p = p0 +

p1 p0

(V V0 ) .

V1 V0

Thus the work the gas must do as it traverses this path is given by the integral

Z V1

p1 p0

L=

p0 +

(V V0 ) dV .

V1 V0

V0

The algebra needed to perform this integration is

V

p1 p0 (V V0 )2 1

p1 p0 (V1 V0 )2

L = p0 (V1 V0 ) +

= p0 (V1 V0 ) + V1 V0

V1 V0

2

2

V0

i

h

p1 p0

1

2

2

2

1

=

(V1 V0 )(p1 + p0 ) .

2

Now V1 V0 < 0 and thus the work is negative and the environment performs work on

the system. Note also that the absolute value of the above expression is the area of the

triangle connecting the three states (V0 , p0 ), (V1 , p1 ), and (V1 , p0 ) and the rectangle beneath

this triangle. Evaluating the above with the given values of p and V gives

1

L = (1.27 2.1) 102m3 (1.99 + 1.15) 105Pa = 1.3 103 m3 Pa .

2

To calculate the heat absorbed by the system we remember that for an ideal gas U(T ) = CV T

and a diatomic gas specifically has CV = 52 R so we have the change in internal energy given

by U = CV T = CV (T1 T0 ) or

5

U = CV (305 291) = CV (14 K) = (8.314J/molK)(14K)(1mol) = 2.9 102J .

2

From the first law of thermodynamics for small changes we have Q = U + W and we

obtain for the heat absorbed by the system

Q = 2.9 102J + (1.3 103 J) = 10.1 102 J = 1.01 1010 erg .

Where we used the unit conversion between ergs and Joules of 1J = 107 erg.

Problem 4

In this problem we have one mole of a diatomic gas undergoing an adiabatic volume expansion. If we define the initial volume to be V0 the final volume V1 is then 1.35V0. For an

adiabatic transformation we have

T V K1 = constant .

(354)

Restricting this expression to connect the two states (T0 , V0 ) and (T1 , V1 ) we obtain

T0 V0K1 = T1 V1K1

(355)

T1 = T0

V0

V1

K1

(356)

We are given the initial temperature of T0 = 18C = 18 + 273.15K = 291.15K, the knowledge

1

.

that the gas is diatomic (so K = 75 ), and the fact that ratio of volumes is given by VV01 = 1.35

From this information we can compute that

V0

V1

K1

= 0.507 .

(357)

With this we finally compute the final temperature as T1 = 291.15K (0.507) = 147.6 K.

Problem 1

Referring to figure, XXX, we first characterize what we know along each path in the p-V

plane and then develop the necessary mathematics. First, paths BD and CA are adiabatic

therefore no head flows through them. Second, along AB and DC the temperature does not

change and since for an ideal gas the internal energy U is a function of temperature only

U = U(T ). Therefore along AB and DC dU = 0 so from the first law we have that dQ = dW

which implies Q = W .

We will solve this problem for the total work performed by the gas by computing the work

along each path in a clockwise fashion beginning with the path AB. To perform this calculation we will require the work performed by an ideal gas along an adiabatic expansion. This

will be calculated first and used in the calculations that follow.

We begin by deriving the work performed during an adiabatic transformation between two

general points in p V space (p1 , V1 ) and (p2 , V2 ). Along an adiabatic transformation of an

ideal gas we have

pV K = constant ,

(358)

or anchoring the constant in the above expression to the point (p1 , V1 ) we have

pV k = p1 V1k

(359)

p = p1

V1

V

K

= p1

V

V1

K

(360)

Thus the work between to points can be calculated in a straight forward manner as

Z V2

W12 =

pdV

V1

Z V2

p1

=

V k dV

V1k

V1

k+1 V2

p1

V

=

V k k + 1

V1

p1 V1k

1k

V2k+1 V1k+1 .

(361)

We now begin with the calculations required for this particular problem. First the work

performed by our ideal gas along the isothermal path AB is given by

WAB = RT2 log(

VB

),

VA

(362)

which when evaluated, using the numbers given in the problem, gives the following

5

WAB = (8.314J/molK)(400K) log( ) = 5352.3J .

1

(363)

Note that this is also equal to the heat absorbed by our engine Q2 , at this state of the cycle.

Now along the path BD, since it is adiabatic we have in terms of variables of this problem

T2 VBK1 = T1 VDK1 .

(364)

VD =

T2 K1

V

T1 B

1/K1

= VB

T2

T1

1/K1

(365)

1/K1

400

VD = 5liters

.

300

Now for a monotonic gas K = 5/3 giving the volume in the D state the value

VD = 7.69 liter .

Using equation 361 we have that for a monotonic gas

(6.65 105Pa)(5 103m3 )5/3

3 3 1 53

3 3 1 53

(7.69

10

m

)

(5

10

m

)

= 1.24 103J .

WBD =

1 53

For practice, the units in this expression work out as follows

2

Pa m5 (m3 ) 3 = Pa m5 m2

= Pa m3

N 3

m

=

m2

= Nm = J

Along the isothermal path DC we have that pV = constant giving in terms of the variables

of this problem the expression

pD V D = pC V C ,

(366)

which when we solve for pC the expression

VD

7.69

5

pC = pD

= 4.32 10 Pa

= 2.158 106 Pa .

VC

1.539

(367)

T2 VAK1 = T1 VCK1 ,

or solving for VC the expression

1/K1

1/K1

T2

4

VC =

VA = 1 liter

= 1.539 liter .

T1

3

(368)

WCA = RT1 log(

7.69

VD

) = (8.314J/molK)(300K) log(

) = 4.01 103J .

VC

1.539

(369)

Note that this equals the heat released by the process through this segment of the cycle or

Q1 . Finally, along the segment CA we have (using the expression for the work performed by

an adiabatic transformation derived above) the following

2.158 106Pa (1.539 103m3 )5/3 3 3 2/3

3 3 23

(10

m

)

(1.539

10

m

)

LCA =

= 1.65 103 J

5

3

Wtotal = WAB + WBD + WDC + WCA = 9.27 103J

(370)

Problem 2

First, convert the given temperatures into Kelvin as follows

T1 = 18 C = 291.15 K

T2 = 400 C = 673.15 K ,

(371)

(372)

then using Fermi Eq. 59 we have a maximum possible efficiency between these two temperatures of

291.15

T1

=1

= 0.567 .

(373)

=1

T2

673.15

Problem 3

Converting the given temperatures into Kelvin we have

0 F = 255.92 K = T1

100 F = 310.92 K = T2 .

(374)

(375)

Then the minimum amount of work will be achieved when the engines operating cycle is

reversible. As such, from Fermi Eq. 60. we have

T2 T1

L=

Q1 .

(376)

T1

With the heat extracted Q1 = 1 cal we obtain, in various units

L =

=

=

=

=

0.2149 Q1

0.2149 cal

0.2149 4.185 107erg

8.99 106 erg

0.899 J .

Where in the above conversions we have used the conversion that 1 erg = 107 J.

Problem 1

We begin by recognizing that 1kg H2 O = 1000 gm H2 O and converting the given temperatures

to Kelvin as follows

T1 = 0 + 273.15 K = 273.15 K

T2 = 100 + 273.15 K = 373.15 K

For liquids Ill make the assumption that Cp CV and is constant. As given in the book

we will take its value to be 1cal/gm. A change in entropy along a reversible path is given by

Z B

dQ

S =

.

(377)

T

A

From the first law we have dU = dQ pdV and a constant volume transformation results

in dU = dQ = CV dT . Since along a constant volume transformation we have the heat ratio

defined by

dQ

= CV

(378)

dT V

Putting this expression into equation 377 results in

Z T2

CV dT

T2

S =

= CV ln( ) .

T

T1

T1

(379)

Which is an expression to be understood as per unit mass. Using the numbers provided for

this problem gives for the entropy change

373.15

)

273.15

= 311.9 cal/K = 311.9 (4.185 107erg/K)

= 1.305 1010erg/K

Problem 2

We are told that a body obeys the following equation of state

pV 1.2 = 109 T 1.1 ,

and asked to find the energy and entropy of such a system as a function of T and V . To

solve this problem in a more general setting consider a body that has an equation of state

given by

pV a = dT b

(380)

With a = 1.2, d = 109 , b = 1.1, and CV = 0.1 cal/deg for this problem. Now the units of V

are liters. Now consider U = U(V, T ) then one can show for a system performing p-V work

that

U

p

=T

p,

V T

T V

which is a nice expression because once an equation of state is specified empirically one can

compute/evaluate

U

,

V T

p=

dTb

,

Va

(381)

therefore

U

V

d b T b1

,

Va

(382)

dbT b1 dT b

dT b

=

(b

1)

= (b 1)p .

Va

Va

Va

(383)

p

T

From this expression integrating U holding T fixed gives the following expression for U(V, T ),

in terms of an arbitrary function of temperature C1

U(V, T ) = (b 1)dT b

V a+1

+ C1 (T ) .

a + 1

1b

Q

U

b1 V

+ C (T ) .

CV

=

= (b 1)dbT

1

T V

T V

1 a V0

CV

(T ) = CV (b 1)dbT

b1

V01b

.

1a

C1 (T ) = CV T (b 1)dT b

V01b

+ C2

1a

U(V, T ) = CV T + (b 1) d T b

(V 1a V01a )

+ C2

1a

(384)

dS =

dU + pdV

1

1

dQ

=

= dU + p dV .

T

T

T

T

(385)

U

U

dU =

dT +

dV ,

T V

V T

in the above expression for dU we obtain for dS

dbT b1 1a

1 dT b

1

1a

b a

CV + (b 1)

(V

V0 ) dT + (b 1)dT V dV +

dV

dS =

T

1a

T Va

CV

dT

T

dT

= CV

T

dT

= CV

T

dT

= CV

T

dS =

(b1 )dbT b2 1a

1

1 dT b

(V

V01a )dT + (b 1)dT bV a dV +

dV

1a

T

T Va

bdT b V a

b(b 1)T b2 dV 1a

(b 1)dbV01a T b2

+

dV +

dT

dT

T

1a

1a

(b 1)dbV01a T b2

d2 T b dV 1a

dT + bdT b1 V a dV +

dT

1a

dT 2 1 a

V 1a

d2 (T b ) V 1a

d(T b ) a

b(b 1)d 0 T b2 dT +

d

dT

+

d

V dV

1a

dT 2 1 a

dT

We can verify our algebra by checking if this is an exact differential as it must be. As such

we must have

d(T b) a

d2 (T b ) V 1a

CV

=

d

+ ...+

d

V

V T

dT 2 1 a

T

dT

which becomes

d2(T b ) a

d2(T b ) a

V

=

d

V

(386)

dT 2

dT 2

which is a true statement. Therefore one can integrate dS if one can find an integrating

factor. Since dS is an exact differential there exists a function S(T, V ) such that

d2 T b V 1a

CV

dV 1a

S

=d 2

+

b(b 1) 0 T b2

(387)

T V

dT 1 a

T

1a

d

and

S

V

S=d

=d

d(T b) a

V .

dT

d(T b) V 1a

+ F (T ) ,

dT 1 a

(388)

(389)

for an arbitrary function F (T ). Taking the temperature derivative of the above gives

d2 (T b ) V a

S

=d

+ F (T )

2

T V

dT 1 a

and setting this equal to equation 387 gives for F (T )

1a

CV

b2 V0

b(b 1)T

d

F (T ) =

T

1a

F (T ) = CV ln(T ) bT b1

V01a

d + S0 .

1a

S(T, V ) = CV ln(T ) +

dbT b1 1a

(V

V01a ) + S0

1a

(390)

Problem 3

From Clapeyrons equation we have

dp

=

dT

T (V2 V1 )

(391)

Here V2 is the specific volume of the gas phase and V1 is the specific volume of liquid phase.

In Kelvin, the boiling temperature for ethyl alcohol is given by T = 351.45K. Assuming

V1 V2 and that the value of V2 for ethyl alcohol is approximately the same as for H2 O of

3

Clapeyrons equation becomes

1677 cm

gm

dp

dT

J

855 gm

3

)

(351.45K)(1677 106 m

gm

J

= 1.45 103 3

m K

Pa

= 1.45 103

.

K

Problem 1

WWX: I have not finished proofreading this section ... start this is page 11 from

the second set of scanned notes

The phase rule v = 2 + n f , saturated solution and a solid dissolved in the in the substitute

have two phase liquid solution and solid (know this is correct page 86 gives examples of salt

in H2 0 and two components n = 2 ( a solid and a liquid component ).

v = 2+22 =2

(392)

therefore we can specify 2 variables T and p arbitrary. I would think that the correct answer

wold be T only. I know that increasing the temperature increases the solvability but am not

sure about the pressure)

Problem 2

I am told the amounts of H2 O and air. Ill assume air contains N2 , O2 , and H2 only and

H2 O vapor, then f equals the number of phases (which is 2), and n equals the number of

components which is 4. We have that

v = 2+42 =4

But we are told the amount of H2 0. and air so we are told

(393)

Problem 3

Now

v(t) = v0 + v1 t + v2 t2

(394)

v0 = 924

v1 = 0.0015

v0 = 0.0000061

(395)

(396)

(397)

The units of T are centigrade, the units of V are volts, and the units of e are Columnbs,

from Page 96 we have

dQ = dU + dL = eU(T ) + ev(T )

(398)

dv

but from the equation of Helmholtz u(T ) = v T dT

, thus the equation of Helmholtz gives

the a functional form for the energy lost per unit charge.

= (v0 + T v1 ) + (v1 2v2 T )t + v2 t2

(399)

(400)

dv

dv

) + ev = eT dT

therefore we need u(T ) actually

Then dQ = e(v T dT

Q = eT

dv

= eT (v1 + 2v2 t)

dT

Chapter 7 (The Thermodynamics of Dilute Solutions)

Chapter 8 (The Entropy Constant)

WWX: I have not finished this section ... end

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