4. Units of Measurements
(1)
1999 "Mars Climate Orbit"
(2) SI unitInternational System of Units
m (meter)
kg (kilogram)
s (second)
1
()
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
()
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
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
()
variable
2 quasi-static process- infinitesimal rate change
irreversible- state ()
* spontaneous process irreversible
()
(cm)
h (cm)
20
10
19.5
36.8
19
64.9
(h+h0) =constant
PV=constant
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
Gas
P/Torr
()
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
2 L 3 3
1 eu k T r 2 d r
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
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
3 critical region
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
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
()
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
2 z slope 0
, B 0, y
P0
P.25
1
ay
1by RT
, y 1
Vm
a, b
z >1
z <1
Example 1.10
1
,
Vm
z
0
y y0
()
P( V, T )
3-dimensional surface
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
P constant
()
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
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
Vc 3b
8a
27bR
a
a
8a
2
Pc
27b 2b 9b
27b 2
1 Pc , Tc , Vc a b
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
PR
P
T
, TR
Pc
Tc
8a
a
PR , V 3b V R , T
TR
2
27 bR
27 b
, VR
V
Vc
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
11
()
1 V
V P T, n
T
V
1
intensive
V
1 nRT 1
ideal gas: T 2
V P P
liquid
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
()
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