()

Chapter1. The Behavior of Gases and Liquids

1.1 Introduction
1. Systems any object that we wish to study
macroscopic , P. V. T
microscopic ,
2. Mathematical Functions

independent variable one to which we can assign a value

dependent variable PV = nRT
V = nRT/P V dependent variable
P, T, n independent variable
P = nRT/V P dependent variable
P = P(T, V, n)
independent variable
P = f (T, V, n)
3. function
(1) 2-D 1 independent variable
P = V -1(nRT)
constant

(2) 3-D 2 independent variables

2-D

4. Units of Measurements
(1)
1999 "Mars Climate Orbit"
(2) SI unitInternational System of Units

m (meter)
kg (kilogram)
s (second)
1

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K (kelvin)
A (ampere)
cd (candela)
mol (mole)
(derived units)

N (Newton)
1 N = 1 kg m s-2
Pa (Pascal)
1 Pa = 1 N m-2 = 1 kg m-1 s-2
J (Joule)
1 J = 1 Nm = 1 kg m2 s-2
(3) Non-SI unit
1 atm

= 101325 Pa ()
= 760 Torr
()
1 bar
= 100000 Pa ()
1 cal = 4.184 J ()
(4)
Avogadro's constant
Ideal gas constant

NAv = 6.022141023 mol-1

R = 8.3145 J K-1 mol-1
= 1.9872 cal K-1 mol-1
= 0.08205 L atm K-1 mol-1
= NAv kB

Boltzmann's constant kB = 1.380710-23 J K-1

5. Problem Solving Techniques

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1.2.
1. System and Surrounding
system: the part of the physical world under consideration
surrounding: all the rest of the universe
system + surrounding = universe
2. Types of Systems
matter

open system

heat

work

closed system

adiabatic system

isolated system

3. systemstate
A. equilibrium state : none of its thermodynamic properties changes with time
( variable )
B. steady state : matter or energy flows, but properties independent of time
flow system P, T, n
C. metastable state : practically no change with time of observation
1 H2 O2
2 supercooled water
3 diamond vs. graphite

4. State Variables (functions) macrostate PTV

(state function state history )
intensive variable independent of mass, can be measured at a point
extensive variable dependent of mass, should be measured as a whole
combine 2 identical systems 2
intensive

extensive

Q
A

S
T
2 extensive variables intensive
= m/VVm = V/n (molar volume)
5. Equation of State variable
P nRT

dependent variable

n, T, V indep. variable

P f (n,T,V ) P(n,T,V )
() 3 (P, V, T, n 3 )
equation of state

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6. Process an occurrence that changes the state of a system

driving force
reversible- direction can be reversed at ant point by some infinitesimal change in the surrounding
1 all intermediate state are quasi-equilibrium state

variable
2 quasi-static process- infinitesimal rate change

irreversible- state ()
* spontaneous process irreversible

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1.3. Real Gas

1. Ideal Gas Law
1660 Robert Boyle P 1
V

(cm)

h (cm)

20

10

19.5

36.8

19

64.9

h0=1033.6 cm for H2O()

(h+h0) =constant
PV=constant

1787 Alexandre Cesar Charles P T at const. V

1802 Joseph Gay-Lussac V T
V V0 1 0 , V0 273 K
0 = 1/267 1/237.15
V100 C V0C K 1.375 ( 373.15/273.15 = 1.366)
T

T0

1
T - T 0 V 0 T T
V V 0 1
0
T0

P
PV nRT

3.661 10

103

-3

N2

3.67

ideal gas

H2
He

3.66
700

2. Virial Equation
(1) ideal gas
z : compressibility compression factor
T
z=

PV m
PV

nR T
RT

const. for all gases

Gas

P/Torr

()

(2) Virial Equation

2

PV
n
n
z=
1 B2 T B3 T
nR T
V
V
1
1
1 B2 (T )
B3 (T )
Vm
Vm

low

n
1
z 1
V

z 1 A2 T P A3 T P 2

2
low P z 1

PVm RT A2 (T ) P A3 (T ) P 2
1
1
1 C2 C3 2
high T z 1
T
T
T

n
n
n
1 , P RT

1 B2 B3
V
V
V

2
2 , z 1 A RT n 1 B n A R 2T 2 n 1 B n

2
2
2
3

V 2
V
V

V
2
n
n

1 A2 RT B2 A2 RT A3 R 2T 2

V
V

2
B3 B2 A2 R T A3 R 2T 2 B2 A3 R 2T 2

A2 B2

A2 B2 ,

B B
A3 3 2

RT

A3

B B

R 2T 2

RT

<> B2(T) interaction potential relate, B 2 T 2 L

2 L 3 3

1 eu k T r 2 d r

for hard sphere

3. van der Waals Equation

an 2
P 2
V

V nb nRT

nRT an 2

V-nb V 2

a
P 2
Vm

Vm b RT

intensive variable

1 P, V
<>
2 ideal gas P + , V

()

b excluded volume

4
1 16
2
2 r 3 r 3 d 3
3
2 3
3

a internal pressure ()

n
attraction
V
2
n
total attraction
V
P = 19.57 atm, V = 1 , T = 300 K

attraction

Cl 2

P = 45.64 atm, V = 1 , T = 600 K

V = 2 , T = 600 K , P = ?
Question : mixture , ?

a a1 x1 2 a12 x1 x 2 a 2 x 2
2

b b1 x1 2b12 x1 x 2 b2 x 2
2

a12

1 1 3
13
a1 a 2 , b12 b1 b2
2

van der Waals eq.: even eq.

1 virial eq. ideal-gas-like case, vdw

2 liq. continuity of state

3 critical region

4 ,

5 a, b (Pc, Tc, Vc) 1.4

4. equation of state

P A 2
(1) Berthlot

TVm

Vmb RT , a A

a
(2) Dieterici
P e a Vm RT Vm b R T , P 2
Vm

a
a
Pe Vm RT
P1 2 P1
Vm R T
Vm P

a
1
P
Vmb RT

V
V
b
T
m
m

1
(4) Redlich - Kwong - Soave
P a T
Vmb RT

V
V
b
m
m

2
T

T
1 m
1
TC

(3) Redlich - Kwong

(5) Beattie - Bridgeman

5parameters

c
PV m RT 1 3
T Vm

0.5%

B
bB
1 0 0
V m V m
7

A0

Vm

a
1
Vm

P No. of pairs

n

V

()

5. equation virial equation :

vdw
B2

ba

B3

b2

TB

RT

Berthlot
b A

Dieterici
ba

RT 2

b2

bR

b 2

B0

RT

ab
a2

RT 2R 2T 2
a

bR

Beattie-Bridgeman

bR

A0
c
3
RT T

A0 a
Bc
B0 b 03
RT
T

Boyle Temp : Boyles Law holds

1 B=0 T

2 z slope 0

, B 0, y
P0

P.25

6. van der Walls Equation z

PVm RT
a V

2 m
RT Vmb Vm RT
V
a
m
Vmb RTVm

1
ay

1by RT

, y 1
Vm

a, b
z >1
z <1

Example 1.10

1
,
Vm

z
0
y y0

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1.4 Coexistence of Phase and the Critical Point

1. PVT surface
species , P-V-T equation of state

P( V, T )
3-dimensional surface

(1) Isotherms ( 3-D 2-D )

isotherm
tie line
Vg , Vl
gas slope liquid slope
law of rectilinear diameter
critical point

T Vl Vg
(liquid gas K.E. liquid)
Vg nRT

Vl

Vg

Critical point : PV curve

strong scattering of light ( Fig. 1.6)
infinite heat capacity
infinite compressibility

P constant

()

(2) Phase diagram

triple point
2-phase coexistence curve
1-phase region
normal f.p. b.p.
liquefy gas without phase
Tc Pc

phase diagram
CO2 triple point 5.112 atm 216.5 K
194.6K 78.5C

2. van der Waals gas critical parameters (Vm V )

P

RT
a
2
Vb V

RT
2a
P
3 0
0

2
Vb V
V T

2P
2 RT
6a
2 0
4 0
3
Vb V
V T
1

V b V

2
3

3Vc3b 2Vc

RTc
2a

0
2
4b
27b 3

Tc

van der Waals equation, Pc

Vc 3b

8a
27bR

a
a
8a
2
Pc
27b 2b 9b
27b 2

1 Pc , Tc , Vc a b

2 van der Waals gas , z

b 4
Vc 12

1
2
a 3PcVc , b Vc
3

PcVc 3
0.375
R Tc 8

zc 0.25~0.3

10

Pc

1 a
3 Vc 2

()

parameter ( Pc , Tc )

vdw

Berthlot

27R 2Tc
64 Pc

RTc

zc

Pc

27R 2Tc
64 Pc

RTc

8Pc

4R 2Tc
e 2 Pc

27b

8Pc

R 2Tc

9 2 3 1 Pc

RTc
e 2 Pc

2 131RT 3P
c
c

2
0.27
e2

a 4b e

3b
8a

Beattie-Bridgeman

Vc
Tc

Dieterici

2b
a

27bR

4bR

3. Law of Corresponding State

,
reduced parameter

PR

P
T
, TR
Pc
Tc

8a
a
PR , V 3b V R , T
TR
2
27 bR
27 b

, VR

V
Vc

van der Waals equation

P 2 Vb RT
V

PV
P 3 c 2c

PcVc

8P V
1
2
b Vc , a 3PcVc , R c c
3
3 Tc

V
8P V
V c c c T

3
3Tc

2
P

V
3 c2 V 1 8 T

V Vc 3 3 Tc
c

3
Pr 2
Vr

1
8
Vr Tr

3 3

universal curve gas

<> vdW Law of Corresponding State
eq. of state Law of Corresponding State
P. 34 Fig. 1.9

11

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4. equation of state state variable

(1) isothermal compressibility

1 V

V P T, n

T
V

1
intensive
V

1 nRT 1
ideal gas: T 2
V P P
liquid

298 K, 1 atm T 4.52 105 bar1

(2) coefficient of thermal expansion

thermal expansivity
1 V

V T P , n

03.98C

ideal gas: 1
T
: 2.57 10 -4 K -1

T , V
T
solid coefficient of linear thermal expansion

1 L

L T P

1
3

L (, P.19)

12

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1.5
1.
df
dx
dx

f f ( x), df

differential of f

df
f ( x h) f ( x )
lim
dx
h
h 0

2. partial differential

derivative of f

( Appendix B)

f f ( x, y, z ) variable
f
f
f
df dx dy dz
z x, y
x y, z
y x, z
partial derivatives
variable constant
dV

nR
nRT
RT
dT 2 dP
dn for ideal gas
P
P
P

P, V, T parameter
V
V
V P , T dV
dT
dP
T P
P T
P
P
PV , T dP
dT
dV
T V
V T
1 dP

dP

V P

dT

V P

dV

P
1
(1)

V T V

P T

() x , y

V
P
T P
(2)
V
T V
P T

V
V P

T P
P T T V

1 dV 0

1 T with E constant

dV
V V P
(3)



dT E T P P T T E

3. General rules :
1
A
(1)
B C B
A C

13

V P V

1
P T T V T P

()

A
A
C
(2)
B

C
C

B
A

C B
C A

A
B

A
A
A X
(3)



,
B C B X X B B C

A B C

1 , cyclic rule


B C C A A B

A X


, constant
X B B C

b
p 2a 2b , A ab
1 a
<>
A
ab A b f a
0
a p

A
A A b
b a 1 ba 0
a p a b b a a p
P

a b
1
P

b
2

V
P
T

V
T V
P T
1 V

V T P

1 V

V P T

14