Specific Heat

Macroscopically, specific heat c , is an intensive property

that represents the amount of heat that needs to be added
to 1 kg of material to raise its temperature by 1oK

δQ KJ
For example : c= units :
MdT kg ⋅o K

The value of c depends on the process of heat addition

For constant volume heat addition:

∆U = δQ − δW
δQ M Mdu = δQ − pdV

Hence define specific heat at constant volume as

δQ Mdu du
c= = = = cV du = cV dT
MdT MdT dT V const

In general cv depends on P and T, so

2 2
u 2 − u1 = ∫1 du = ∫1 cV ( P, T ) dT

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For constant pressure heat addition:

δQ M

∆U = δQ − W
Mdu = δQ − pdV
Mdu = δQ − p ( Mdv)
δQ = M (du + Pdv)

Define new property, enthalpy h

h = u + Pv → dh = du + Pdv + vdP

For constant P process dP=0, so dh = du + Pdv

Substituting into the definition for c

δQ M (du + Pdv) dh
c= = = = cP dh = cP dT
MdT Mdt dT P const

In general cP also depends on P and T, so

h2 − h1 = ∫12 dh = ∫12 c P ( P, T )dT

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Ideal Gas Assumption

For an ideal gas cV and cP only vary with T, not P

u 2 − u1 = ∫12 cv (T ) dT
h2 − h1 = ∫12 c P (T ) dT

Need absolute u and h. Set T2 to T and T1 to Tref

h2 − h1 = h(T ) − h(Tref ) = ∫TT c P (T )dT

ref

Take Tref =0 (absolute zero temperature) where h=0

h(T ) = ∫0T c P (T ) dT
h (T ) = ∫0T c P (T )dT

for an ideal gas pv = RT

∴ h = u + pv = u + RT → u = h − RT

u (T ) = ∫0T c P (T ) dT − RT
u (T ) = ∫0T c P (T ) dT − R T

cp values are tabulated in Table A-20 and Table A-21

gives an empirical relation for (c p / R ) as a function of T
for various gases.
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Enthalpy and Internal energy as a function of T for air is
given in Table A-22, and for other gases in A-23.

Get cV from cP differentiate h = u + RT with respect to T

dh du
= + R → c P (T ) = cV (T ) + R
dT dT
dh du
= + R → c P (T ) = cV (T ) + R
dT dT

Note : Since R > 0 and cV > 0 Æ cp > cV

The specific heat ratio k is commonly used, for ideal gas

cP
k (T ) = since c P > cV → k > 1 see Table A - 20
cV

For a substance with molar mass µ if you know k at a

specific temperature can get cp and cV

c P (T ) = cV (T ) + R c P (T ) = cV (T ) + R
c P (T ) R R
= 1+ c P (T ) = +R
cV (T ) cV (T ) K (T ) − 1
R K (T ) R
cV (T ) = c P (T ) =
K (T ) − 1 K (T ) − 1

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Example:
A tank contains 0.042 m3 of oxygen (O2) at 21C and 15 MPa.
Determine the mass of the oxygen, in kg, using
a) the compressibility chart
b) ideal gas model
Comment on the applicability of the ideal gas model

V= 0.042 m3
T= 21 C (294 K)
O2
P= 15 MPa (150 bar)

a) From table A-1for oxygen: molar mass µ= 32 kg/kmol,

Tc= 126K, Pc=50.5 bar

P 150 bar T 294 K

PR = = = 2.97 ; TR = = = 1.91
Pc 50.5 bar Tc 126 K

From the Generalized Compressibility Chart Z ≈ 0.92

ZRT 0.92(8314/32 J/kg ⋅ K)(294K)

v= = = 0.0047 kg/m 3

P 150x10 5 N/m 2

V 0.042 m 3
M = = 3
= 8.94 kg
v 0.0047 /m /kg

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b) Assuming ideal gas

PV (150x10 5 N/m 2 )(0.042m 3 )

M = = = 8.24 kg
RT (8314/32 J/kg ⋅ K)(294K)
Assuming the mass obtained from the chart is correct, the ideal gas model under predicts the

mass by about 8%, not bad!

Do the same problem with carbon dioxide (CO2):

P 150 bar T 294 K

a) PR = = = 2.03 ; TR = = = 0.97
Pc 73.9 bar Tc 304 K

From the Generalized Compressibility Chart Z ≈ 0.3

v = 0.0011 m3/kg Æ M = 38.2 kg

b) Mideal = 11.34 kg

Assuming the mass obtained from the chart is correct, the

ideal gas model under predicts the mass by about 70%,
bad!

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Example:

A piston-cylinder assembly contains 1 kg of nitrogen gas (N2).

The gas expands from an initial state where T1= 700K and P1= 5
bar to a final state where P2= 2 bar. During the process the
pressure and specific volume are related by Pv1.3= const.
Assuming ideal gas behaviour and neglecting KE and PE effects,
determine the heat transfer during the process, in KJ.

P 1
Q Pv1.3= const
N2

2
P1= 5 bar P2= 2 bar
T1= 700K
v
∆U = Q − W
Q = ∆U + W

P2V2 − P1V1
W = ∫12 pdV =
1− n

Recall, for an ideal gas PV = MRT

MR(T2 -T1 )
∫1
2
pdV = need T2
1− n

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 P1v1 Pv P  const  P  const 
R= = 2 2 → 1  1 / n  = 2  1 / n 
T1 T2 T1  P1  T2  P2 

n −1 n −1 n −1 n −1
n −1
P1 n
P n
T2  P2  n v
n
 n T2  v1 
= 2
→ =   = 1
n
 → =  
T1 T2 T1  P1  v
2  T1  v2 
0.3
 2 bar  1.3
T2 =   (700K) = 567K
 5 bar 

MR(T2 -T1 )
W=
1− n
1 kg(8.314/28 kJ/kg ⋅ K)(567 - 700)K
= = +132kJ
1 − 1.3

Note: work is positive Æ work done by the system

The molar internal energy for nitrogen from Table A-23:

u (700K ) = 14,784 kJ/kmol

u (567K ) = 11,858 kJ/kmol

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 u −u 
∆U = M (u 2 − u1 ) = M  2 1 
 µ 
 11,858 - 14,784 kJ/kmol 
= 1 kg  = −104.5 kJ
 28 kg/kmol 

Q= ∆U + W = (-104.5 kJ) + (132 kJ)= +27.5 kJ

Note: heat transfer is positiveÆ heat transferred into the

system

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Constant Specific Heat Assumption

This assumption can be made if the specific heat does not

vary much in the temperature range of interest, use
average values c~V and c~P such that:

u 2 − u1 = ∫TT cV (T )dT = c~V ∫TT dT = c~V (T2 − T1 )

1
2

1
2

h − h = ∫T c (T )dT = c~ ∫T dT = c~ (T − T )
2 1
2

T1 p P T1
2

P 2 1

the average value is taken to be

c (T ) + cV (T2 ) c (T ) + c P (T2 )
c~V = V 1 c~P = P 1
2 2

Example:

Recalculate ∆U in last example assuming constant

specific heat
The specific heats for nitrogen from Table A-20 for the two temperatures are

cV (700K) = 0.801 kJ/kg ⋅ K

cV (567K) = 0.771 kJ/kg ⋅ K

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The average value over the temperature range is thus

~ (0.801 + 0.771)
cV = = 0.786 kJ/kg ⋅ K
2
∆U = M (u − u ) = Mc~ (T − T )
2 1 V 2 1

= 1 kg (0.786kJ/kg ⋅ K)(567 - 700)K

= - 104.5 kJ

The value for ∆U obtained using Table A-23 which takes

into account the change in cV with temperature is exactly
the same!!

If tables are not available can approximate cV by using the

specific heat ratio K, which in the temperature range of
300K to 1000K, is taken to be constant (see Table A-20):

Diatomic molecules Æ K= 7/5= 1.4

(N2, O2, H2, CO, “Air”,…)

Monatomic molecules Æ K=5/3=1.67

(Ar, He, Ne,…)

R 8.314/28 kJ/kg ⋅ K
cV = = = 0.742 kJ/kg ⋅ K
K −1 1.4 - 1

compared to 0.786 kJ/kgK calculated above

70
Incompressible Assumption

A substance is incompressible if there is negligible

change in specific volume with change in pressure,
e.g., liquids and solids

The specific internal energy of an incompressible

substance does not vary much with pressure, therefore the
specific heat only depends on temperature

du (T )
cV (T ) =
dT v const

By definition enthalpy varies both with P and T

h(P,T) = u(T) + Pv

For incompressible v is constant, differentiating with

respect to T while maintaining P constant yields,

dh(T ) du (T )
=
dT P const dT v const

cP = c v = c

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 u 2 − u1 = ∫12 c(T )dT

Also, ∆h = ∆(u + Pv)

h2 − h1 = (u 2 − u1 ) + ( P2 v2 − P1v1 )

h2 − h1 = ∫12 c(T ) dT + v( P2 − P1 )

Two special cases:

i) Constant pressure heat addition into an incompressible

substance (P= const.)

h2 − h1 = ∫12 c(T )dT

ii) Isothermal heat addition into an incompressible

substance (T= const.)

h2 − h1 = v( P2 − P1 )

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Approximating enthalpy in the compressed liquid
region of steam tables

Want to get enthalpy at (P*, T*) without using

compressible liquid tables
Liquid at Liquid at
(P*,T*) Saturation line (P*,T*)
P* isobar
P* isobar
T* T1=T* P1(= Psat(T*)) isobar

Saturation state (P1,T1)

Consider the isothermal process (incompressible) from

(P1,T1) Æ (P*,T*) we now know h*- h1=v(P*- P1)

h* = h1 + v( P * − P1 )

h( P*, T *) = h f sat (T *) + v f sat (T *)[( P * − Psat (T *))]

This gives a more accurate result than just taking

h( P*, T *) = h f sat (T *) as proposed earlier for u(P*,T*)

The last term is a correction which is normally small

because vfsat is very small

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