Equations 52 and 53 in the notes are the key equations for the solution of this problem.

A) The first terms in Eqs. 52 and 53 in the notes are the ideal gas enthalpy and entropy at
reference state, 300 K and 1 bar. These data are given in the problem statement:

J J
H0ig ≔ 18115 ⋅ ―― S0ig ≔ 295.976 ⋅ ―――
mol mol ⋅ K

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B) The second terms in Eqs. 52 and 53 in the notes are the temperature effects on H and S of an ideal
gas. We can use the MathCad program established earlier, ICPH and ICPS, for this calculation.

T0 ≔ 300 ⋅ K T ≔ 360 ⋅ K J
R ≔ 8.314 ⋅ ―――
mol ⋅ K

A ≔ 1.7765 B ≔ 33.037 ⋅ 10 −3 ⋅ K −1 C ≔ 0 ⋅ 10 −6 ⋅ K −2 D ≔ 0 ⋅ K2

T
τ (T0 , T) ≔ ―
T0

B
H2 (T0 , T , B) ≔ ―⋅ T0 ⋅ (τ (T0 , T) + 1)
2

C ⎛ 2 ⎞
H3 (T0 , T , C) ≔ ―⋅ T0 2 ⋅ ⎝τ (T0 , T) + τ (T0 , T) + 1⎠
3

D
H4 (T0 , T , D) ≔ ―――――
τ (T0 , T) ⋅ T0 2

MCPH (T0 , T , A , B , C , D) ≔ A + H2 (T0 , T , B) + H3 (T0 , T , C) + H4 (T0 , T , D)

ICPH (T0 , T , A , B , C , D) ≔ MCPH (T0 , T , A , B , C , D) ⋅ (T − T0)

MCPH (T0 , T , A , B , C , D) = 12.679

ICPH (T0 , T , A , B , C , D) = 760.723 K

D
S2 (T0 , T , C , D) ≔ C ⋅ T0 2 + ――――― 2
τ (T0 , T) ⋅ T0 2

τ (T0 , T) + 1
S3 (T0 , T) ≔ ――――
2

τ (T0 , T) − 1
S4 (T0 , T) ≔ ――――
ln (τ (T0 , T))

MCPS (T0 , T , A , B , C , D) ≔ A + (B ⋅ T0 + S2 (T0 , T , C , D) ⋅ S3 (T0 , T)) ⋅ S4 (T0 , T)

ICPS (T0 , T , A , B , C , D) ≔ MCPS (T0 , T , A , B , C , D) ⋅ ln (τ (T0 , T))

HT ≔ R ⋅ ICPH (T0 , T , A , B , C , D)
( )
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 ST ≔ R ⋅ ICPS (T0 , T , A , B , C , D)

kg ⋅ m 2 J
HT = ⎛⎝6.325 ⋅ 10 3 ⎞⎠ ――― ST = 19.173 ―――
s 2 ⋅ mol mol ⋅ K

C) The third term in Eq. 53 in the notes is the pressure effect on S of an ideal gas. Note that the
pressure effect on H of an ideal gas is zero.

bar ≔ 10 5 ⋅ Pa

P0 ≔ 1 ⋅ bar P ≔ 15.41 ⋅ bar

J ⎛ P ⎞
HP ≔ 0 ⋅ ―― SP ≔ −R ⋅ ln ⎜―⎟
mol ⎝ P0 ⎠

J
SP = −22.739 ―――
mol ⋅ K

D) The third term in Eq. 52 and the fourth in Eq. 53 in the notes represent the departure from the
ideal gas; these terms, in turn, can be estimated based on Eqs. 50 and 51 in the notes and the
experimentally measured values in the problem statement.
⎡ 2.590 ⎤
ORIGIN ≔ 1 ⎢ 2.470 ⎥
⎢ ⎥
2.186
i ≔ 1 ‥ 11 ⎢ ⎥
⎢ 1.759 ⎥
⎡ 0 ⎤ ⎡ 1.78 ⎤ ⎢ 1.591 ⎥
⎢ 0.1 ⎥ ⎢ 1.70 ⎥ Z12 ≔ ⎢ 1.544 ⎥
⎢ ⎥ ⎢ ⎥ i
0.5 1.514 ⎢ 1.552 ⎥
⎢ ⎥ ⎢ ⎥ ⎢ 1.592 ⎥
⎢ 2 ⎥ ⎢ 1.293 ⎥ ⎢ ⎥
⎢ 4 ⎥ ⎢ 1.29 ⎥ ⎢ 1.658 ⎥
p1 ≔ ⎢ 6 ⎥ Z11 ≔ ⎢ 1.395 ⎥ ⎢ 1.750 ⎥
i i
⎢ 8 ⎥ ⎢ 1.560 ⎥ ⎢⎣ 1.835 ⎥⎦
⎢ 10 ⎥ ⎢ 1.777 ⎥
⎢ ⎥ ⎢ ⎥
⎢ 12 ⎥ ⎢ 2.073 ⎥
⎢ 14 ⎥ ⎢ 2.432 ⎥
⎢⎣ 15.41 ⎥⎦ ⎢⎣ 2.72 ⎥⎦

Z2 ≔ Z12 ⋅ 10 −2 ⋅ bar −1
p ≔ p1 ⋅ bar Z1 ≔ Z11 ⋅ 10 −4 ⋅ K −1 ⋅ bar −1 i i
i i i i

Now, we have to conduct numerical integration by trapezoidal rule:

i ≔ 1 ‥ 10
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 Now, we have to conduct numerical integration by trapezoidal rule:
i ≔ 1 ‥ 10

h ≔p −p
i i+1 i h h
i i
Int1 ≔ ⎛Z1 + Z1 ⎞ ⋅ ― Int2 ≔ ⎛Z2 + Z2 ⎞ ⋅ ―
i ⎝ i i + 1⎠ 2 i ⎝ i i + 1⎠ 2

I1 ≔ ∑ Int1 I2 ≔ ∑ Int2
i i
i i

1
I1 = 0.003 ― I2 = 0.261
K

HR ≔ −R ⋅ T 2 ⋅ I1 SR ≔ −R ⋅ T ⋅ I1 + R ⋅ I2

J J
HR = 0 ―― SR = 0 ―――
mol mol ⋅ K

E) Finally, we can add these terms together and obtain the desired H and S:

H ≔ H0ig + HT + HP + HR S ≔ S0ig + ST + SP + SR

J J
H = ⎛⎝2.444 ⋅ 10 4 ⎞⎠ ―― S = 292.41 ―――
mol mol ⋅ K

Although this example illustrates a very accurate experimental procedure for the acquisition of
enthalpy and entropy, data have to be collected for individual species and it is a time-consuming
procedure. The generalized correlation methods discussed later in the chapter, however, use the
theory of corresponding of state as their basis for the prediction of enthalpy and entropy and one
needs only Tc, Pc and  in the prediction.

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