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5.60 Thermodynamics & Kinetics
prin! "00#
$or in%ormation a&out citin! these materia's or our Terms o% (se) *isit: http://ocw.mit.edu/ter ms.
5.60 Spring 2008 Lecture #1 page 1
Thermodynamics
Th e rm o dynami c s :
Describes macroscopic properties of
equilibrium systems
Entirely Empirical
Built on 4 Laws and simple mathematics
0
th
Law Defines Temperature T!
"
st
Law Defines Ener#y $!
%
nd
Law Defines Entropy &!
'
rd
Law (i)es *umerical +alue to Entropy
These laws are $*,+E-&.LL/ +.L, D 0 they canno t be circum)ented1
D e fi n i t i o ns :
&ystem: The part of the $ni)erse that we choose to study
&urroundin#s: The rest of the $ni)erse
Boundary: The surface di)idin# the &ystem from the
&urroundin#s
&ystems can be:
2pen: 3ass and Ener#y can transfer between the &ystem
and the &urroundin#s
4losed: Ener#y can transfer between the &ystem and the
&urroundin#s0 but *2T mass
,solated: *either 3ass nor Ener#y can transfer between
the &ystem and the &urroundin#s
D e sc r ibin# syst em s r e q u ir e s :
. few macroscopic properties: p0 T0 +0 n0 m0 5
6nowled#e if &ystem is 7omo#eneous or 7etero#eneous
6nowled#e if &ystem is in Equilibrium &tate
6nowled#e of the number of components
Two c la ss e s o f 8 r oper t i e s :
E9tensi)e: Depend on the si:e of the system
n0 m0 +05!
,ntensi)e: ,ndependent of the si:e of the system
T0 p0 V =
V
05!
n
The & ta t e of a &y st e m at Equi l ib r ium:
Defined by the collection of all macroscopic properties that
are described by &tate )ariables p0 n0 T0 +05!
;,*DE8E*DE*T of the 7,&T2-/ of the &/&TE3<
=or a one>component &ystem0 all that is required is n and %
)ariables1 .ll other properties then follow1
V = f (n, p, T) or p = g(n, V, T)
*otation:
' 7
%
#0 " bar0 "00 4!
' moles #as p?" bar T?"00 4
n?'!
% 4l
%
#0 @ L0 @0 4! 0 @ .r s0 @ bar0 @0 6!
5.60 Spring 2008 Lecture #1 page 4
4 h an # e o f & t a t e : Transformations!
*otation:
' 7
%
#0 @ bar0 "00 4!
initial state
? ' 7
%
#0 " bar0 @0 4!
final state
8ath: &equence of intermediate states
5
p (bar)
1
50
100
T +K,
8rocess: Describes the 8ath
> -e)ersible always in Equilibrium!
> ,rre)ersible defines direction of time!
> .diabatic no heat transfer between system and
surroundin#s!
> ,sobaric constant pressure!
> ,sothermal constant temperature!
> 4onstant +olume
>
>
>
Thermal Equilibrium heat stops flowin#!
A B A B A
B
Ahen a hot obBect is placed in thermal contact with a cold obBect0
heat flows from the warmer to the cooler obBect1 This continues
until they are in thermal equilibrium the heat flow stops!1 .t this
point0 both bodies are said to ha)e the same temperature1
This intuiti)ely strai#htforward idea is formali:ed in the 0
th
Law of
thermodynamics and is made practical throu#h the de)elopment of
thermometers and temperature scales1
CE-2Dth L.A of Thermodynamics
If
A
and
B
are in thermal equilibrium and
B
and
C
are in thermal equilibrium0
then
A
and
C
are in thermal equilibrium1
Consequence of the zeroth law:
B
acts liEe a thermometer0 and
A
0
B
0 and
C
are
all at the same temperature1
5.60 Spring 2008 Lecture #1 page 6
2pera t i o na l definition of temperature t!
*eed: "! substance
%! property that depends on t
'! reference points
4! interpolation scheme between ref1 pts1
E9ample : ,deal (as Thermometer with the 4elsius scale1
Based on BoyleDs Law
lim
(
p+
)
= constant = f (t )
p 0 t
for fixed t depend on t
the substance is a #as
f (t ) is the property
the boilin# point
(
t
b
= "004
)
and free:in# point (
t
f
= 04
) of
water are the reference points
the interpolation is linear
p 0
f(t)=f(0 !)(1+At)
-.perim enta'
resu't:
A " 0.00#660$ " 1%2&#.15
/"01.25 0 200 C
*ote :
(
t = %F'1"@ 4
)
is
special
t = %F'1"@ 4 is called the absolute :ero0
???????
This su##ests definin# a new temperature scale 6el)in!
T
(
6
)
= t
(
4
)
+
%F'1"@
T ? 06 corresponds to absolute :ero
(
t = %F'1"@ 4
)
???????
Better reference points used for the 6el)in scale today are
T ? 06 absolute :ero! and T
tp
? %F'1"G6 triple point of 7
%
2!
f (T )
p 0
f (T ) =
tp
T
%F'1"G
or

lim
(
p+
)

f(T
tp
)
lim
(
p+
)
=

p '0 tp

0 T(()
0 "01.263 T
tp
,d e a l (as e s
BoyleDs Law and the 6el)in scale

lim
(
p+
)

lim p+ =

p 0 tp

T -T )alid for al l #ases for p 0

p 0
T

%F'1"G

define
the #as constant
.n id e a l #as obeys the e9pression p+ = -T at all pressures
the #as molecules do not interact!

)i*
(
pV
)

R =

p 0
tp

= 8.#1451
J
#as constant!
2&#.16 K mol

The Ideal gas law
p+ = -T or p+ =
n-T
This is an e9ample of an equation of state
+ = f
(
n0 p0T
)
(
)
5.60 Spring 2008 Lecture #1 page $
Equations of state
, DE.L ( . & L. A : p+ = n-T p+ = -T
3i9ture of ideal #ases comprisin# n
i
moles of each
p =
n
i
-T
i
+
n
i
8artial pressure of i
th
#as
th
p = p
Total
=

p
i
H I
i
=
i
n
mole fraction of i #as
p =
n
i
i
n
p = I
i
p
DaltonDs Law
- e al ( a se s >> do not necessarily obey ideal #as law
a! 4ompressibility factor
+
p+ = C-T C =
real

+
ideal
+
real
>+
ideal
+
real
<+
ideal
b! +irial E9pansion
#enerally ne#lect
p+
= C (T ) = " +
B
(
T
)
+
4
(
T
)
+ +
-T + +
%
.s p 00+ 0 ideal #as B ? 0 ideal #as
ne#lect 4 and hi#her order terms!
7i#h T -epulsions dominate C J "
Low T .ttractions dominate C K "
5.60 Spring 2008 Lecture #1 page 10
c! )an d e r Aaa l s Equati o n o f s t ate
only two parameters0 deri)ed from molecular concepts
=irst assume hard sphere molecules
p+ = -T becomes p
(
+

b
)
= -T
*ow put in attraction
&o p
=

-T

becomes p
=

-T
a

%

+ b

+ b

+
-earran#in#

p +
a

+
(
+ b
)
= -T