43_ GENERAL STRATEGY FOR DERIVING
THERMODYNAMIC RELATIONS.
inthe previous section provide the bass for
(
own Se. 42 a efor fe ion elaine ete
and pressure is *
sesmn ase Star vear
eee
fnctions thus far defied is given in Table 4.4
thes are introduced as more compien clases of s}slems are encountered andthe
pendent variable, since these variables are most frequently encountered in
forall the other state function in Table 4.4 a Fane
ents ag leis ce i een
ad Zr derived wt tf ves probed in is ton
‘These relationships are the reciprocal relation me
429)
(
2), (i), (i),43,1 Entropy and Volume Relations to T and P
hip Between ts volume, temperature,
veva.p) a
The corresponding differential relation, analogous
av Mars nap
‘Te coefficient relations for this equation give
oC) (3)
sn be expressed in terms ofthe experine
nd -
“The paral des
variables and
to temperature and pressre
‘Consider no the analogous problem forthe entony
a 433)
aS= Mar + war
‘cwaton can be writen a partial derivatives so that.
as (28) are(2
ar), (Fe) 4”
439
“The second coecen,
relations, Recall Bq (4.26)
v= (8), --Gi),—
valuation of requires shor thermodynamic aga
sy been evalu in the consideeton of Maxwell
435)
reversible process, he second law connects the heat absorbed with the
ange in entropy:
30m = Tas ep
3) (8),
‘presare proces, for which AP =0, ean be writen
*
tme=1 (2) an
Wah equation (4.34)
80m = 7
“Te eat absorbed fora const
430
‘constant pressre process are the
eat capacity at constant pressure
BQeur =CrdTr (419)
Comparison of these two expressions for heat sbsorbed at consent pressure demon:
sts thatthe coefficients of dT must be the same quantity in both equations. I is
‘cvelaed that
46:
- "
Creat (ys
)-4
Iain for he vaiaton of ereopy with temperate
‘Measurements of there
tant forthe experimental ev
aa
sesan) tse Sar—vedr
rand a are known a functions of temperature and re
)
au)
nthe process used to determine Cy, the own variables are the temperature, which
SQ mv = Cray
“The heat sorbed ir velated
a the sate fonction S = SCT.)
‘is measured, ad the volume, which is held cons
to the enropy changeot the sytem which
3nominees wenn BS
“To conver Fa. (4.6) forthe enthalpy to «fonction of 7 and P,substute for a8,
a
eer vat] var
wed in detemining Cy, 6V = 0 and
sd collect ers
Hen,P) dt =cyaT +V0—TeNd? (442)
‘Sinan, a, 4.8) is ensily converted toa function of T and P by subsiting for
as
asy=(®) an
ir),
the stcond law as embodied in Eq
Fm = F450 = 7 (,
AF w Sat — Pua = VAP)
Bonen ems
Fak) dh =-(4PVe)dT + PveAP
i Gite fee eneey fenton fs sey expressed in ems of the independent
ible Tand Pin the vorsion orginally deriv
“Tis collection ofall state fanetons expressed in terms of T and P just derived
compa
as)
in these equations contain the following factors:
au = Tas - Pav as
TP which ae the independent variables specified in any
Experi Cr, assumed o be available in
N=O.P) dw =Tassvar
Sand V, which ean be evalated as functions of T and, given, B nd Cr
Fee) af = -sar Pav aa
the intl and inl slates for» process traversed by a sytem are species
heir temperatare and pressure, knowledge of the values of, Band Cy permite
USP) dv =(Cp~PVaMT + VIPR-TavdP (Ast)encorncwams moras 57
1 funetions accompanyi
by the fact that they
1 Bguaing ike terms
MoXp AM My = Zr
MoXp AN Yew Zr
im which Xr. Yr ZrsXes¥p, and Zp are obtained)
are expressed in terns ofthese variables.
rie erors are clearly €
osedtwith thi acti since
bemodynamic qua
Vand 7. es found
AZ m= MUXrdT + XpdP)4N UydT + Yd]
coetcims, Xp. Xp. Yr. ¥p are the colficients of and in the
ons for dX and d? in Table 4,
4, Collecting terms
42 SIM AN y]dT 4M Xp AN YLdP
5. Obtain 2 » 207.) from Table 45
2 = 2ydT + ZpaP
listed under steps 4 and Sar alemate expressions for 2 = (7?)
‘he coefficients of dT and dP in bot equations are respectively,
@), — G,begins with «verbal satemen
sesa.y)
as= Mary Nav ase Mar nev
4s = MaP + W(VedT ~ Var)
Santee gen 2 co oe
wine a 6 is NVa=Cp/T M—NVB =
MeNVaece/T —1p=—Ve emus
(i) <7
H-(8) (8%)
“The check, Ths, the equ aon Is
CPB _ye)ary
a= (Ge- a) er +
9)
fn Heimtoxs free
‘ha vohone
Ferry)
ar =Mar+nav
dF = MAP -4N(VadT ~VBAP)
dP = NVaaT + (Mt - WV BAP
af = ~(S + PVaMiT + PVBAP
Nae (5+ PVM NYB= PVE
‘he genera relation that
(Cy mentioned in Set. 4.1.2. By inspection, the coeticent ofa
(sr), (6-4)
[was shown Eq, (440) thet this oeticint is related to Cy
a8)
ar),
ins Bor MCV = PVITKUPICID = V
forsave for
oto:
au = Mas 4 Nav
Tate 45
(Cr/T oT ~ Vad NWVadT ~ vA)
Tae 45
aH = Cpa 4 VN Taye
Irena of rstonsconsined iTable 45, ln uch ese reaange the gore
aption ofa ef he pend varie
sesr¥)
pation by B andthe boston bya
MCPAIT + NVeR = CoB
as
4. Soe for a
arm Zas- Zoav as»
hero (ore%) soon cos
Te 4,
Ths, an 25a,
bes ae tows forthe nye,
he problem oe he process cased aS » 0
of hi eqetion fen62 nemnonancsmasnenis co
on fo an Ideal Gas
come wnat worsaras 63
To. fo ane
fequenty ecure in ayes of ; : c= cr= ae as)
eos monic ch gu ols ut sng slo ti fed at
tons eae) = 30 aay
Aa tm Cy bah same it ds Ine his vam E45 ein
f te consponng vai or Cr
s sn
gece
. aan
v
(455) JIM conti of canbe igi by ean
nthe stn, hi goin ed va=ce-rv (2) =cp—n= cv
‘system containing 1 mole of substance, then x = 1 and Pva=Cr~PV (7) =Co—R=O
rverr 36
as the molar volume of the gas (volume occupied by one *
he experiment vate cm be copie or lows Arey
the definition of the volume coefficient of the 7 “ i a
apt (2%) 2! ry (a) ot
ween (57), > ar | \@-z |
am .
of compres, :
Piet gw) == 1a (er ol fo ea! gas a for a0 eer satin The ge in
v ary (ae), oa 7 ternal enesay of an ideal gas for any process can, without exception, be computed
ro Ba. 4.52),
‘A similar reso can be obisined for the enthalpy function. Recall Ea. (442)
“The kinetic theory of gates demonstrates that the heat capacity of an idea
fom Table 4.5,
indepen
their
Hanh) aH CAT +v(~TaydP aa)
the efficient of A? is Found to be
va-raav[i-r(2)}0and Bg, (4.42) becomes
gas) CpdT 40-4? Cpa
hey occur at constant entropy. (Ths conclasion is
iabaic process since entropy i prodaced within the system)
example 48, One ol of el gs nally temper 7a copying olame
i comprested everably and abate fame, Compute the Bal
tener, Tf te yen,
Men the varies T= 1839)
oem we ete resins
he general case in Example 46, yelding
Ts Te
re Las. Teav ax
Soe
‘Since the proce under sy is enrop, 5 = Oa
=-Zhevs (es)
CoB §
ora ea eo = 1/T and
mina P dough the equation
aT
TCA
»(i)
[Beret] -orwn ne “
-an %
i inal temperature at the reversible adiabatic compression is
Iropy when a monstomic ideal gat experi ‘The final temper the end of | oe npr
cay)
Nextt i i tg an, alle tha tai gas ep diab
raperare dog, Ts phenomena he bs or ome eigen cys.
onpenion of the gx ae Ws wempertre: us» yee Pp
‘The rest examph the daar: proce
‘Then whateverAlgcteaic manipltion ofthis equation simplest:
wey”
relatenship expressed in ems
PV%= cont, 4)
epoca: the ever adit copes:
feat variate to deste ie path
favorite sample problem in every
om [Lom
«Ve
5
one ay
emncomamcnanas wonaons 67
Since no transfer occur between system snd ts suroundings, the contribution to
expands mus be entropy production xsing
ofthe proces that eviderly eur far fom eq
decoding tothe second lw
To complete the specifica
this process, 5Q = 4W = 0: Ths,
the itera! energy of the system U
the inter
anne change during the proces, and AU =
temperature, Eq (458, Since the ine
as= Sars Sev 2
Tart
the isothermal reversible proces comer evauteo nd
Pn 8,
r= Bavy = Bavyemwoomasec wus we nmanort 69
core 2
Relationship reir: $= $V), Ba (449)
Cob