First Law of Thermodynamics

State Functions
- A State Function is a thermodynamic quantity whose value depends only on the
state at the moment, i. e., the temperature, pressure, volume, etc
- The value of a state function is independent of the history of the system.
- Temperature is an example of a state function.
- The fact that temperature is a state function is extremely useful because it we can
measure the temperature chane in the system by !nowin the initial temperature
and the final temperature.
- "n other words, we don#t need all of the nitty-ritty detail of a process to measure
the chane in the value of a state function.
- "n contrast, we do need all of the nitty-ritty details to measure the heat or the
wor! of a system.
$eversibility
A reversible process is a process where the effects of followin a thermodynamic
path can be undone be exactly reversin the path.
An easier definition is a process that is always at equilibrium even when underoin a
chane.
%hase chanes and chemical equilibria are examples of reversible processes.
"deally the composition throuhout the system must be homoeneous.
- This requirement implies that the no gradients, currents or eddys can exist.
- To eliminate all inhomoeneities, a reversible process must occur infinitely
slow&
- Thus no truly reversible processes exist. 'owever, many systems are
approximately reversible. And assumin reversible processes will reatly aid
our calculations of various thermodynamic state functions.
$eversibility durin pressure chanes ensures that
p ( pex
That is, the pressure on the inside of the container is always equal to the pressure
exerted on the outside of the container.
)
Theorem of *aximum +or!
The maximum amount of wor! that can be extracted from an
expansion process occurs under reversible conditions.
Thus the theorem implies that durin an irreversible expansion, some of the enery is
lost as heat rather than wor!. The inhomoeneities ,currents, radients and eddys- in
pressure that occur durin an irreversible process are responsible for the heat.
"nitial .efinitions of /nery and /nery Transfer
"nternal /nery
- Sum of the !inetic and potential enery in a sample of matter.
*icroscopic modes of "nternal /nery ,01
th
century view-
- derees of freedom for enery storae
translational
rotational
librational 2 vibrations caused by intermolecular forces
vibrational
electronic
nuclear, etc
- more specifics in second semester
- unnecessary for understandin of thermodynamics but sometimes helpful.
*acroscopic view of internal enery ,)3
th
century view-
- A reservoir of enery within the sample.
- The details of the enery are un!nown.
"nternal enery is a state function.
+or!
$ecall the definition of wor! from classical mechanics.
w F dl

r r
*icroscopically, wor! involves the concerted motion of molecules ,that is, molecules
movin in one direction.-
+or! is a transfer of enery, not a quantity of enery.
+or! is not a state function.
-calculation of wor! depends on thermodynamic path ,as seen from definition-
0
A more thermodynamically useful rearranement ,let F ( pA and d4 ( dlA- is
ex
w p d4

- the neative sin is a sin convention ,discussed below-

- pex is the external pressure ,the pressure outside the container-
- pex is used in definition because we really do not !now what !ind of pressures
develop durin a thermodynamic chane.
- i.e., pressure currents and eddies are li!ely for an arbitrary chane.
5ther forms of wor! are possible
w / dq

/lectrical wor!
( )
w / d 4%

r r
%olari6ation wor! ,e.., pie6oelectricity-
w dA

Surface tension
w d

Twistin wor!
Sign conventions for work
-w 2 wor! done by system ,expansion for p4 wor!-
7w 2 wor! done on the system ,compression for p4 wor!-
'eat
- macroscopically heat is a thermal enery transfer
- enery transfer usually characteri6ed by temperature and the 6eroth law of
thermodynamics.
- microscopically heat transfer comes from
- inelastic collisions
- enery transfer from one molecule to another in multiple ,every- direction
Sign conventions for heat
-q 2 heat transferred away from body ,heat lost-
7q 2 heat transferred into body ,heat ained-
8
First 9aw of Thermodynamics
The physicists that studied enery chanes reconi6ed that the enery of an ob:ect
could be chaned via heat or wor!.
;ames ;oule demonstrated experimentally the law of conservation of energy, that is,
that enery is not ained or lost, but merely transferred from one ob:ect to another.
The law of conservation of enery is also !nown as the first law of
thermodynamics. Since enery chanes can be expressed only as heat or wor!, the
first law of thermodynamics has the mathematical expression
< q w +
Subtle points to ma!e=
)- q and w are enery chanes, writin q and w is improper.
- +e can#t refer to ob:ect havin an amount of heat or wor!. The ob:ect has
internal enery, enthalpy, free enery, etc
0- The form of the first law of thermodynamics depends on the sin convention
chosen for heat and wor!. 5lder texts state that
< q w
> however, the sin
convention for wor! is different,
ex
w p d4 +

.ifferential Form of the First 9aw

The differential form of the first law is written as
d<?q 7?w
The differential forms of heat and wor! are written with the slash to emphasi6e that
they are inexact differentials.
@onstant volume heat
.urin a constant volume process, w ( 1. Therefore
v
< q
That is, constant volume heat is equal to a chane in the free enery.
A
*easureable thermodynamic quantities
Thermal expansivity
The thermal expansivity is the measure of how a material chanes its volume as
the temperature chanes.
p
) 4
4 T
_

,
Isothermal compressibility
T
) 4
4 p
_

,
The isothermal compressibility is the measure of how a material chanes its
volume as the pressure chanes. Almost always, volume will decrease with
increasin pressure, therefore, a neative sin is included in the definition to
allow for the tabulation a positive values.
Both definitions modify an extensive chane,
p
4
T
_

,
or
T
4
p
_

,
, into an
intensive chane by dividin the chane by the volume.
/nthalpy
Bac!round
"n order to fully explain his ideas of free enery, ;osiah +illard Cibbs needed to
construct an enery state function that had the definition
' ( < 7 %4
Cibbs named the quantity the heat content because a chane in the quantity
corresponded to heat ained or lost by a system at constant pressure provided no non-
p4 wor! is bein done, that is.
p
' q
Damerlinh 5nnes eventually named the function, ' the enthalpy and the name
stuc!.
E
Heat capacity
- 'eat is proportional to mass.
- 'eat is proportional to temperature difference.
- %roportionality constant for a specific substance is the heat capacity or specific
heat.
q m@ T
.efinition of @onstant %ressure 'eat @apacity 2 @p
Since constant pressure heat is a chane in enthalpy, the constant pressure heat
capacity can be rewritten as
p
p
'
@
T
_

,
This quantity is one of the easily measurable quantities that is very important in
thermodynamics.
.efinition of @onstant 4olume 'eat @apacity 2 @v
Since constant volume heat is a chane in internal enery, the constant volume heat
capacity can be rewritten as
v
v
<
@
T
_

,
This quantity is another one of the easily measurable quantities that we will use a
reat deal in thermodynamics studies.
$elationship between @p and @4
5ne way of examinin the difference between internal enery and enthalpy is by
examinin the difference between the constant pressure heat capacity and the constant
volume heat capacity.
( ) ( )
p 4
p 4 4 p 4
p p
p p 4
< %4 %4 ' < < < <
@ @
T T T T T T T
< 4 <
%
T T T
+ _ _ _ _ _ _ _
+


, , , , ,
, ,
_ _ _
+


, , ,
F
At this point, we want to find another expression for
p
<
T
_

,
since it is not an easily
measurable quantity. +e can find an alternative expression for
p
<
T
_

,
based the total
differential of the internal enery.
The internal enery is a function of temperature and volume, thus the total differential is
4 T
< <
d< dT d4
T 4
_ _
+


, ,
.ividin the total differential by dT under constant pressure conditions yields
p 4 p T p 4 T p
< < T < 4 < < 4
T T T 4 T T 4 T
_ _ _ _ _ _ _ _
+ +


, , , , , , , ,
Two of the partial derivatives in this expression should be familiar=
4
4
<
@
T
_

,
and
p
4
4
T
_

,
. $emember the thermal expansivity is
p
) 4
4 T
_

,
9et us substitute our result into the oriinal equation for @p 2 @4 ,
p 4
p p 4 4 T p p 4
T p p T p T
< 4 < < < 4 4 <
@ @ % %
T T T T 4 T T T
< 4 4 < 4 <
% % 4 %
4 T T 4 T 4
1
_ _ _ _ _ _ _ _
+ + +
1


, , , , , , , , 1
]
1 1 _ _ _ _ _ _
+ + +
1 1

, , , , , ,
] ]
What is the relationship between Cp C! for an ideal gas"
p p
) 4 ) n$T ) n$ n$
4 T 4 T p 4 p p4
_ _



, ,
p 4
T T T
T T
< n$ < n$ <
@ @ 4 p 4 p p
4 p4 4 p 4
n$ < n$ ) <
p n$ )
p 4 p p 4
1 1 1 _ _ _
+ + +
1 1 1

, , ,
] ] ]
1 1 _ _
+ +
1 1

, ,
] ]
$emember that for an ideal as
T
<
1
4
_

,
, therefore
G
p 4
T
) <
@ @ n$ ) n$
p 4
1 _
+
1

,
]
The relationship can be rewritten in terms of molar heat capacities.
p 4
@ @ $
% %
This relationship is very important and worth memori6in.
Why is Cp greater than C!"
- 'eat capacity is substance#s capacity to store enery.
- A substance that can store enery via wor! has a reater heat capacity than a
substance that has its volume !ept constant.
'eat $eexamined
"sothermal 'eat
dq @dT q 1
"sochoric 'eat
4 4
dq @ dT q @ dT

"f @4 is independent of temperature, ,fair assumption for small temperature chanes-,

then
( )
4 4 4 0 ) 4
q @ dT @ dT @ T T @ T

"sobaric 'eat
p p
dq @ dT q @ dT

Adiabatic 'eat
By definition, q ( 1
All of the above results are free from assumptions ,unless noted-.
Thermochemistry
H
/xtent of $eaction
To monitor the proress, a variable !nown as the extant of reaction is defined as
i i,1
i
n n

where ni is the number of moles of chemical species i, ni,1 is the initial number of
moles of chemical species i and i is the stoichiometric coefficient of the chemical
species i for the specific reaction occurrin.
+hen the extent of reaction is defined this way, the value of the extant of reaction
does not depend on the chemical species used to examine the state.
/xample= @onsider the reaction %A ,s- 7 E 50 ,- 0 %05E ,s-. Suppose we start
with 8 moles of phosphorus and )E moles of oxyen.
a- +hat is the extant of reaction when A moles of %05E has been createdI
i i,1
i
n n
Amol 1mol
0
0

Jote= 'ow much %A has been consumed to create A moles of %05EI A= 0 moles.
b- +hat is the extant of reaction when 0 moles of phosphorus has reactedI
i i,1
i
n n
)mol 8mol
0
)

The definition includes the stoichiometric coefficient to put the chanes of the all the
chemical species on an equal footin.
Soon we will be dealin reaction eneries and other quantities specific to reactions.
The reaction eneries need to be intensive quantities and yet each chemical species
may have a different amount. Thus reaction eneries are defined with respect to the
extent of reaction so that the specific chemical species is not important, but the
reaction as a whole is important.
Standard States
3
Standard #ressure - p

Thermodynamic quantities are measured with respect to a pressure of ) bar ,)11.111

!%a-
Standard Temperature - T

Thermodynamic quantities are measured with respect to a temperature of 0E @

,03H.)E D-
Standard Concentration- c

Thermodynamic quantities are measured with respect to a concentration of )m ,that is

) molal-.
- *olal is used as a concentration unit rather than molar because molal is
independent of temperature.
$iological Standard State
The bioloical standard state is a pressure of ) bar, a temperature of 8G @ and
p' of G, ,that is K'
7
L ( ).1 )1
-G
-.
'ess# 9aw
)1
Since enthalpy is a state function, we can choose more than one thermodynamic path
to calculate a state function.
For chemical chanes, 'ess# 9aw states that the enthalpy of a reaction can be
calculated from the enthalpies of all of the chemical step processes needed for the
chemical reaction.
"n other words, if reactions can be added toether to form a resultant reaction, then
enthalpies of the step reactions can be added to find a resultant enthalpy of reaction.
/xample= @alculate the enthalpy of reaction for the followin reaction=
0 Al,s- 7 8 @l0,- 0 Al@l8,s-, iven the reactions below.
0 Al,s- 7 F '@l,aq- 0 Al@l8,aq- 7 8 '0,- ' ( -)1A3 !;Mmol
'@l,- '@l,aq- ' ( -GA.H !;Mmol
'0,- 7 @l0,- 0 '@l,- ' ( -)HE !;Mmol
Al@l8,s- Al@l8,aq- ' ( -808 !;Mmol
$earrane the equations such that their sum is the reaction of interest.
0 Al,s- 7 F '@l,aq- 0 Al@l8,aq- 7 8 '0,- ' ( -)1A3 !;Mmol
FK'@l,- '@l,aq-L ' ( FK-GA.H !;MmolL
8K'0,- 7 @l0,- 0 '@l,-L ' ( 8K-)HE !;MmolL
0KAl@l8,aq- Al@l8,s-L ' ( 0K7808 !;MmolL
0 Al,s- 7 F '@l,aq- 7 F '@l,- 7 8 '0,- 7 8 @l0,- 7 0 Al@l8,aq-
0 Al@l8,aq- 7 8 '0,- 7 F '@l,aq- 7 F '@l,- 7 0 Al@l8,s-
' ( -)1A3 !;Mmol 7 FK-GA.H !;MmolL 7 8K-)HE !;MmolL 7 0K7808 !;MmolL
( -)A1F !;Mmol
0 Al,s- 7 8 @l0,- 0 Al@l8,s- ' ( -)A1F !;Mmol
/nthalpy of Formation
))
The enthalpy of formation is the enthalpy of a formation reaction for a particular
substance.
A formation reaction is that where a compound is formed from elements in the
naturally occurrin state.
0 @,s- 7 8 '0,- 7 N 50,- @0'E5' ,l-
N %A ,s- 7 EM0 50,- %05E,s-
G Fe,s- 7 )H @,s- 7 3 J0,- FeAKFe,@J-FL8 ,s-
%nthalpy of formation of the elements
By definition, the enthalpy of formation of an element in its natural state is 6ero.
f',B,s-- ( 1 !;Mmol f',@,raphite-- ( 1 !;Mmol f',Br0,l-- ( 1 !;Mmol
f',SH,s-- ( 1 !;Mmol f',A,s-- ( 1 !;Mmol f',Oe,-- ( 1 !;Mmol
$eaction enthalpies can be calculated as a stoichiometric sum of enthalpies of
formation. This technique is an application of 'ess# law.
/xample= @alculate the enthalpy of reaction for the followin reaction=
@'8@55',l- 7 @A'35',l- @A'355@@'8,l- 7 '05,l-,
iven the reactions below.
0 @,s- 7 0 '0,- 7 50,- @'8@55',l- ' ( - AH8.E0 !;Mmol
A @,s- 7 E '0,- 7 N 50,- @A'35',l- ' ( - 80H !;Mmol
F @,s- 7 F '0,- 7 50,- @A'355@@'8,l-' ( - F13.F !;Mmol
'0,- 7 N 50,- '05,l- ' ( - 0HE.H8 !;Mmol
Jote all of the above reactions are formation reactions.
$earrane the equations such that their sum is the reaction of interest.
@'8@55',l- 0 @,s- 7 0 '0,- 7 50,- ' ( 7 AH8.E0 !;Mmol
@A'35',l- A @,s- 7 E '0,- 7 N 50,- ' ( 7 80H !;Mmol
F @,s- 7 F '0,- 7 50,- @A'355@@'8,l-' ( - F13.F !;Mmol
'0,- 7 N 50,- '05,l- ' ( - 0HE.H8 !;Mmol
@'8@55',l- 7 @A'35',l- 7 F @,s- 7 F '0,- 7 50,- 7 '0,- 7 N 50,-
0 @,s- 7 0 '0,- 7 50,- 7 A @,s- 7 E '0,- 7 N 50,- 7 @A'355@@'8,l- 7 '05,l-
' ( 7 AH8.E0 !;Mmol 7 80H !;Mmol - F13.F !;Mmol - 0HE.H8 !;Mmol ( - HA !;Mmol
@'8@55',l- 7 @A'35',l- @A'355@@'8,l- 7 '05,l- ' ( - HA !;Mmol
)0
@alorimetry
@onstant %ressure @alorimeter
- coffee cup calorimeter
- open to atmosphere
- appropriate for solution chemistry
@onstant 4olume @alorimeter
- bomb calorimeter
- sealed and isolated
- appropriate for as phase chemistry
Adiabatic @alorimeter
- heat measured by temperature needed to !eep thermal enery constant.
Process of measuring heat of combustion with bomb calorimeter
). *ass wic! used to start combustion.
0. *ass water used to absorb heat.
8. *ass standard ,ben6oic acid- to be combusted
A. Add water to combustion chamber to ensure that water from combustion will be
in liquid phase.
E. 9oad standard and seal
F. Fill combustion chamber with oxyen , 0E atm-
G. Bein combustion and record temperature chane of water.
H. @alculate heat capacity of calorimeter from standard
- need to account for heat of wic!, and heat capacity of water.
3. $epeat process with sample.
- with heat from wic!, heat from the water and heat from the calorimeter, the
heat of combustion of sample can be calculated.
'ess# law is often used to the enthalpy of formation of a substance after its enthalpy
of combustion has been calculated.
/xample= 1.E08 of the military explosive, cyclotetramethylenetetranitramine
,'*O-, @A'HJH5H is combusted in a bomb ,&- calorimeter and an internal
enery chane of 2 A.F01 !; is measured. @alculate the enthalpy of
formation for '*O.
First write a balanced equation for its complete combustion.
@A'HJH5H,s- 7 0 50,- A @50,- 7 A '05,l- 7 A J0,-
Jext calculate the molar internal enery of reaction from the experimental data.
A.F0!; 03F.)EE
0F)F!; mol
1.E08 mol

)8
To calculate the enthalpy of the reaction, we need to return the definition of enthalpy.
( ) ( ) ( ) ' < %4 < n$T < n $T + + +
$eexaminin the balanced chemical equation, we see that
H moles 2 0 moles ( F moles of as has been produced.
@A'HJH5H,s- 7 0 50,- A @50,- 7 A '05,l- 7 A J0,-
( )
1.11H8)A!;
' < n $T 0F)F!; mol F 03H.)ED
mol D
0.AGH!;
0F)F!; mol F 0F)F!; mol )A.HG!; mol 0F1)!; mol
mol
_
+ +

,
_
+ +

,
The molar enthalpy of reaction can also be written in terms of the molar enthalpies of
formation.
A f',@50,-- 7 A f','05,l-- - f',@A'HJH5H,s-- ( r'
$earraned, the equation becomes,
f',@A'HJH5H,s-- ( A f',@50,-- 7 A f','05,l-- - r'
From table, we find the enthalpies of formation for @50,- and '05,l-
f',@A'HJH5H,s-- ( A ,-838.E !;Mmol- 7 A ,-0HE.H !;Mmol- - ,-0F1) !;Mmol-
( -))F !;Mmol
Temperature .ependence of "nternal /nery and /nthalpy
$ecall that
4
4
<
@
T
_

,
and p
p
'
@
T
_

,
These relationships imply that we can find the internal enery or enthalpy at a
nonstandard temperature as lon as we !now the heat capacity.
4
d< @ dT
and
p
d' @ dT
"nteratin both sides of these equations yields
4
< @ dT

and
p
' @ dT

)A
For lare temperature chanes, we can#t assume that the heat capacity is independent
of temperature. Thus to calculate the internal enery or enthalpy at a non6ero
temperature, we need the temperature dependence of the heat capacity.
/xample= @alculate the chane in enthalpy of '0 ,- from 8G8 D to )111 D, iven
that the constant pressure heat capacity has the form
0
p
@ d eT fT

+ +

where d ( 0G.0H ;MD mol, e ( 1.1180F ;MD
0
mol and f ( 1.111E1 ; DMmol.
( )
( ) ( )
( ) ( ) ( )
)111 )111 )111
0 0
)111 D 8G8 D p
8G8 8G8 8G8
0
)111 )111 )111 0 0
8G8 8G8 8G8
0
0
' ' ' @ dT d eT fT dT d dT eT dT fT dT
eT f e ) )
d TP P P d )111 8G8 )111 8G8 0f
0 T 0 )111 8G8
1.1180F; D mol
0G.0H; D mol F0GD HF1HG)D
0
0 1.111E1

+ + + +
_
+ +

,

( ) ( )
)
F
; D mol 1.11)FH)1D
)G)1E; mol )A18; mol ).FH )1 ; mol )HE1H; mol )H.E)!; mol

+ +
Dirchoff#s law
( ) ( )
T
1
r r i p,i
i
03H
' T ' 03HD @ dT +

That is by ta!in a stoichiometric sum of the heat capacities and interatin over the
temperature rane, we can find the correction to the reaction enthalpy at a non
standard state temperature.
/xample= AG) !;Mmol is the reaction enthalpy under standard conditions for the
followin reaction= 0 Fe058,s- 7 8 @,s- A Fe,s- 7 8 @50,-. +hat is
the reaction enthalpy at )111 DI
)E
Accordin to the J"ST +ebboo! "nternet site, the constant pressure heat capacities of
the chemical species in the above smeltin process can be fitted accordin to the
Shumate equation,
0 8 0
p
@ A BT @T .T /T

+ + + +
The values for A, B, @, . and / for each species are iven below.
A B @ . /
Fe058 38.A8H8A 1.)1H8EH -E.1HFAE )1
-E
0.EF )1
-H
-)F)1111
@ )1.FH 1 1 1 1
@50 0A.33G8E 1.1EE)HG -8.8F3)A )1
-E
G.3E )1
-3
-)8G111
Fe )H.A0HFH 1.10AFA8 -H.3) )1
-F
3.FF )1
-3
-)0F11
Sum -G1.0133 1.1AGA)H -8.E1 )1
-E
).)8 )1
-H
0GF0)GA
( ) ( ) ( )
( )
)111D
1 0 8 0
r r i i i i i i
i
03HD
1 )111 0 )111 8 )111 8 )111 ) )111 i i i
r i i 03H 03H 03H 03H i 03H
i
' )111D ' 03HD A B T @ T . T / T dT
B @ .
' 03HD A T P T P T P T P / T P
0 8 A

+ + + + +
_
+ + + +

,

( ) ( ) ( )
( )
( )
( )
( )
( )
( )
0 0
r
E H
8 8 A A
1.1AGA)H AG)!;
' )111D G1.0133 )111 03H )111 03H
mol 0
8.E1 )1 ).)8 )1
) )
)111 03H )111 03H 0GF0)GA
8 A )111 03H

+ +

_
+ +

,
( )
r
AG)!; A3.8!; 0).F!; 8A.)!; )).0!; F.E!; A)8.3!;
' )111D
mol mol mol mol mol mol mol
+ +
Dirchoff#s 9aw can be stated with in a differential form as well.
"nclude
4
4
<
@
T
_

,
and p
p
'
@
T
_

,
Bond /nthalpies
A bond enthalpy is the enery needed to separate two atoms.
Tabulated bond enthalpies are averae values calculated from the dissociation of
many different compounds.
Thus tabulated bond enthalpies are approximate values.
Q'owever, they can be useful for approximatin enthalpies of reaction because
most of the chemical enery of a compound is held in its bonds.Q
+or! $eexamined
"sochoric +or!
)F
p4 wor! involves a volume chane.
ex
w p d4

Since a constant volume process has no volume chane, w ( 1 if there is no other

wor! ,no non-p4 wor!-.
Jo other assumptions have been made about the system.
"sobaric +or!
Since the pressure is constant, it has no dependence on the volume. Thus the pressure
can pulled out of the interal. Subsequently, the interal of d4 is 40 2 4) ( 4
( )
ex ex ex 0 ) ex
w p d4 p d4 p 4 4 p 4

The only other assumption made is that the system does not have any non-p4 wor!.
"sothermal +or!
"n eneral we need to !now the relationship between pressure and volume to perform
the calculation, i.e, we need an equation of state. 9et us do the calculation for an
ideal as under reversible conditions.
0
ex
)
n$T d4 4
w p d4 p d4 d4 n$T n$Tln
4 4 4
_


,

Jote restrictions on the applicability of the calculation.
). no other non-p4 wor!
0. ideal as
8. reversible conditions
Adiabatic +or!
d<?q 7?w d< ?w w <
Jo assumptions made&
$efrieration and the ;oule-Thomson coefficient
;oule coefficient -
;
<
T
4
_

,
)G
- internal pressure
q ( 1, w ( 1 < ( 1 isoeneretic process
;oule-Thomson coefficient -
;T
'
T
p
_

,
- isoenthalpic, adiabatic
- ( 1 for an ideal as
Classic %xperimental &pparatus
- measure ;T directly.
f
i
4 1
f i i f i i f f
4 1
f i i i f f i
< < < p d4 p d4 p 4 p 4
< p 4 < p 4 ' '



'odern %xperimental &pparatus
- measure ;T via
T
'
p
_

,

)H
- use isothermal conditions rather adiabatic conditions.
isothermal conditions= T) ( T0
T T
T p p
' '
T p p
' '
T p ' T ) T T
)
p ' ' p ' T p @
' T T
_ _


_ _ _ _ , ,


_ _ _
, ,
, ,


, , ,
T
;T
p
'
T
@
_

,

Isoenthalps on T( p plot)
- inversion temperature
- R 1 for substance to be used as a refrierant
- temperature must decrease as pressure decreases.
)3
$eal Cases $eexamined
@alculations on van der +aals as
- p4 wor!
ex
w p d4

01
0
0
n$T an
p
4 b 4

0 0
ex 0 0
0 0
) 0 )
n$T an n$T an
w p d4 p d4 d4 d4 d4
4 b 4 4 b 4
4 b ) )
n$Tln an
4 b 4 4
_
+


,
_ _

, ,

- .ifference in heat capacities
p v
p v
' <
@ @
T T
_ _



, ,
T 4 p T 4
p T p 4 p T p 4
4 p T
< < ) < <
d< d4 dT d< d4 dT
4 T T 4 T
< < 4 < T < 4 <
T 4 T T T 4 T T
< < <
T T 4
_ _ _ _ _
+ +


, , , ,
,
_ _ _ _ _ _ _ _
+ +


, , , , , , , ,
_ _ _



, , ,
p
4
T
_

,
( )
p p p p
p
p4 ' < < 4
' < p4 p
T T T T T
_ _ _ _ _
+ + +


, , , ,
,
[ ]
p v
p p p T p
p T p p T
T
p T T
< 4 < < 4
@ @ p
T T T 4 T
4 < 4 4 <
p p
T 4 T T 4
4 < <
p 4 p 4 p
T 4 4
1
_ _ _ _ _
+
1


, , , , , 1
]
1 _ _ _ _ _
+ +
1

, , , , ,
]
1 1 _ _ _
+ + +
1 1

, , ,
] ]
"nternal /nery $eexamined
+hy is < ( qv under isochoric conditionsI
ex 4
d<?q 7?w d< ?q - p d4 d< ?q < q
0)
Assumin no non-p4 wor!.
"sobaric "nternal /nery
v ex v ex v
d<?q 7?w d< @ dT p d4 < @ dT p d4 @ dT p 4

Jote= no assumptions about the equation of state.
"sochoric "nternal /nery
ex v v
d<?q 7?w d< ?q p d4 d< ?q < @ dT q

Jote= assumption of no non-p4 wor!

"sothermal "nternal /nery
v
d<?q 7?w ( @ dT
dT 1 d< 1

/nthalpy $eexamined
+hy is ' ( qp under isobaric conditionsI
( )
p
' < p4 d' d< d p4 (?q 7?w7pd47 vdp
d' (?q 7-pd47pd47 vdp d' ?q ' q
+ +

00
Assumin no non-p4 wor! and reversible conditions
"sobaric /nthalpy
( )
p p
' < p4 d' d< d p4 (?q 7?w7pd47 vdp
d' (?q pd47pd4 d' ?q ' @ dT q
+ +

Assumin no non-p4 wor! and reversible conditions

"sochoric /nthalpy
( )
p
' < p4 d' d< d p4 (?q 7?w7pd47 vdp
d' (?q pd47pd47 vdp d' ?q 7 vdp ' @ dT vdp
+ +


For ideal as under reversible conditions
p p
n$T
' @ dT vdp @ dT dp
p


+hy not
0
p
)
p
' @ dT n$Tln
p

I
- temperature has a dependence on the pressure.
"sothermal /nthalpy
( )
p
' < p4 d' d< d p4 ( @ dT ' 1 + +
Important* &ll of the above enthalpies assume that the system has no non(p! work
and reversible conditions +so that # , #ex-
Summary
"sothermal T ( 1
"sobaric p ( 1
"sochoric 4 ( 1
Adiabatic q ( 1
08
.efinition of wor!=
ex
w p d4

.efinitions for heat= qp ( ' q4 ( <

Sin conventions for heat and wor!.
-w 2 wor! done by system ,expansion for p4 wor!-
7w 2 wor! done on the system ,compression for p4 wor!-
-q 2 heat transferred away from body ,heat lost-
7q 2 heat transferred into body ,heat ained-
$eversibility
p ( pex
/xtent of $eaction
i i,1
i
n n

.efinition of 'eat @apacities

p
p p
q '
@
T T
_ _



, ,
v
v v
q <
@
T T
_ _



, ,
First 9aw=
ex
d<?q ?w < q w < @dT p d4 + +
%artial .erivatives to be acquainted with= , , @p, @v, T, ;, ;T
p
) 4
4 T
_

,
T
) 4
4 p
_

,
p
p
'
@
T
_

,
v
v
<
@
T
_

,

;
<
T
4
_

,
;T
'
T
p
_

,

and internal pressure
T
T
<
4
_

,
,equals 6ero for ideal as-
Jatural variables of < and ' and total differentials
"nternal enery can be expressed as a function of 4 and T <,4,T-
/nthalpy can be expressed as a function of p and T ',p,T-
- both of these functional dependences are not unique
- will consider other natural variables in the next chapter.
0A
Total differential can be expressed as
4 T
< <
d< dT d4
T 4
_ _
+


, ,
p
T
' '
d' dT dp
T p
_ _
+


,
,
'ess# law
Temperature .ependence of /nthalpy and "nternal /nery
4
< @ dT

and
p
' @ dT

Dirchoff#s law
( ) ( )
T
1
r r i p,i
i
03H
' T ' 03HD @ dT +

4
4
<
@
T
_

,
and p
p
'
@
T
_

,
*iscellaneous Applications of 'eat @apacities
p 4
@ @ $
% %
p
v
@
@

0E