Numerical Problems

BT2061: Biochemical Thermodynamics

M. Hamsa Priya

M. Hamsa Priya BT2061:Problems 1 / 51

 Material and Energy Balance

Problem 1

N2 gas is being removed from a high pressure storage tank through a

device that removes 1% of the current content of the tank each minute. If
the tank initially contains 1000 moles of the gas, how much will remain at
the end of 20 minutes?

M. Hamsa Priya BT2061:Problems 2 / 51

 Material and Energy Balance

Problem 2

As a result of a chemical spill, chloroform is evaporating at the rate of 1

gm/minute into a room that is 6 m × 6 m × 3 m in size and ventilation
rate of 10 m3 /min.
a. Compute the steady state concentration of chloroform in the room
b. Assuming the air in the room is initially free of chloroform, compute the
time necessary for chloroform to reach 95% of the steady state
concentration

M. Hamsa Priya BT2061:Problems 3 / 51

 Material and Energy Balance

Problem 3

The following reaction occurs in air:

2NO + O2 → 2NO2
 
dCNO
At 20◦ C the rate of this reaction is = −1.4 × 104 C2NO CO2 for t
dt
in seconds and concentration in kmol/m3 . The reaction occurs in a
constant volume 2-L vessel, and the initial concentration of NO is 1
kmol/m3 and that of O2 is 3 kmol/m3
a. If 0.5 mol of NO reacts, how much NO2 is produced?
b. Determine how long it would take for 0.5 mol of NO to have reacted.

M. Hamsa Priya BT2061:Problems 4 / 51

 Material and Energy Balance

Problem 4

One mole of a gas at a temperature of 25◦ C and a pressure of 1 bar is to

be heated and compressed in a frictionless piston and cylinder to 300◦ C
and 10 bar. Compute the heat and work required along each of the
following paths. Assume gas to be an ideal gas with C∗P = 38 J/(mol K)
Path A: Isothermal (constant temperature) compression to 10 bar, then
isobaric (constant pressure) heating to 300◦ C
Path B: Isobaric heating to 300◦ C followed by isothermal compression to
10 bar
C∗
Path C: A compression in which PVγ = constant where γ = P∗ followed
CV
by an isobaric cooling or heating, if necessary to 300◦ C.

M. Hamsa Priya BT2061:Problems 5 / 51

 Material and Energy Balance

Problem 5

Stem at 500 bar and 600◦ C is to undergo a Joule-Thompson expansion to

atmospheric pressure. What will be the temperature of the stem after
expansion? What would be the downstream temperature if the steam were
replaced by an ideal gas.

M. Hamsa Priya BT2061:Problems 6 / 51

 Material and Energy Balance

Problem 6

A well-insulated storage tank of 60 m3 contains 200 L of liquid water at

75◦ C. The rest of the tank contains steam in equilibrium with the water.
Spent process steam at 2 bar and 90% quality enters the storage tank
until the pressure in the tank reaches 2 bar. Assuming that the heat losses
from the system to the tank and the environment are negligible, calculate
the total amount of steam that enters the tank during the filling process
and the fraction of liquid water present at the end of the process.

M. Hamsa Priya BT2061:Problems 7 / 51

 Material and Energy Balance

Problem 7

A 0.01 m3 cylinder containing nitrogen gas initially at a pressure of 200

bar and 250 K is connected to another cylinder 0.005 m3 in volume, which
is initially evacuated. A valve between the two cylinders is opened until
the pressure in the cylinders equalize. Find the final temperature and
pressure in each cylinder if there is no heat flow into or out of the cylinder.
You may assume that there is no heat transfer between the gas and the
cylinder walls and that the gas is ideal with a constant-pressure heat
capacity of 30 J/mol K.

M. Hamsa Priya BT2061:Problems 8 / 51

 Material and Energy Balance

Problem 8

Assume that experimental measurements for a certain organism have

shown that cells can convert two-thirds (wt/wt) of the substrate carbon
(alkane or glucose) to biomass.
a. Calculate the stoichiometric coefficients for the following biological
reactions:
Hexadecane:
C16 H34 + aO2 + bNH3 → c(C4.4 H7.3 N0.86 O1.2 ) + dH2 O + eCO2
Glucose:
C6 H12 O6 + aO2 + bNH3 → c(C4.4 H7.3 N0.86 O1.2 ) + dH2 O + eCO2
b. Calculate the yield coefficients YX/S (g dw cell/g substrate), YO2 /S (g
dw cell/g O2 ) for both reactions.

M. Hamsa Priya BT2061:Problems 9 / 51

 Material and Energy Balance

Problem 9

Succinic acid (HOOC–CH2 –CH2 –COOH) is useful as a starting material in

the manufacture of solvents and polymers. It has been suggested that it
can be manufactured from glucose (C6 H12 O6 ) through the following
biochemical reaction:
1 8 1
Glucose + CO2 → Succinic acid + H2 O
7 7 7
a. Write the formulae for glucose and succinic acid on C-mole basis
representation?
b. Is this reaction stoichiometry possible?
c. Estimate the heat released per C-mole of glucose consumed.
d. What fraction of the Gibbs free energy of the glucose appears in the
succinic acid?

M. Hamsa Priya BT2061:Problems 10 / 51

 Includes Entropy Balance

Problem 10

A gas cylinder of 1 m3 volume containing nitrogen initially at a pressure of

40 bar and a temperature of 200 K is depressurized to 20 bar by venting
out some gas. Find the final temperature of the gas. Assume gas to be an
ideal gas with C∗p = 29.3J/molK. Assume no heat flow into or out of the
cylinder or between gas and the cylinder.

M. Hamsa Priya BT2061:Problems 11 / 51

 Includes Entropy Balance

Problem 11

A 5 kg copper ball at 75◦ C is dropped into 12 kg of water, initially at 5◦ C,

in a well-insulated container.
a. Find the common temperature of the water and copper ball after the
passage of a long period of time
b. What is the entropy change of the water in going from its initial to final
state? Of the ball? Of the composite system of water and ball? (Data: Cp
(copper) = 0.5 J/g K and Cp (water) = 4.2 J/g K)

M. Hamsa Priya BT2061:Problems 12 / 51

 Includes Entropy Balance

Problem 12
a. A steam turbine in a process industry is designed to accept 4500 kg/hr
of steam at 60 bar and 500◦ C and exhaust the steam at 10 bar. Assuming
that the turbine is adiabatic and has been well designed (so that there is
no entropy generation), compute the exit temperature of the steam and
the power generated by the turbine.
b. The efficiency of a turbine is defined to be the ratio of the work
actually obtained from the turbine to the work that would be obtained if
the turbine operated isentropically between the same inlet and exit
pressures. If the turbine in part (a) is adiabatic but only 80% efficient,
what would be the exit temperature of the steam? At what rate would
entropy be generated within the turbine?
c. In off-peak hours the power output of the turbine in part (a) (100%
efficient) is decreased by adjusting a throttling valve that reduces the
turbine inlet steam pressure to 30 bar while keeping the flow rate constant.
Compute the temperature of the steam entering the turbine, the steam
temperature at the turbine exit, and the power output of the turbine
M. Hamsa Priya BT2061:Problems 13 / 51
 Includes Entropy Balance

Problem 13

A rigid, isolated container 300 L in volume is divided into two parts by a

partition. One part is 100 L in volume and contains nitrogen at a pressure
of 200 kPa and a temperature of 100◦ C. The other part, 200 L in volume,
contains nitrogen at a pressure of 2 MPa and a temperature of 200◦ C. If
the partition breaks and a sufficiently long time elapses for the
temperature and pressure to become uniform within the container,
assuming that there is no heat transfer to the container and that nitrogen
is an ideal gas with C∗p = 30 J/molK.
a. What is the final temperature and pressure of gas in the container?
b. How much entropy is generated in the process?

M. Hamsa Priya BT2061:Problems 14 / 51

 Real Gases

Problem 14

By measuring the temperature change accompanying a differential volume

change in a free expansion across a valveand  separately
 in areversible
∂T ∂T
adiabatic expansion, the two derivatives and can be
∂V H ∂V S
experimentally evaluated.
a. Develop expressions for these derivatives in terms of the more
fundamental quantities
b. Evaluate these derivatives for a van der Waals fluid

M. Hamsa Priya BT2061:Problems 15 / 51

 Real Gases

Problem 15

A tank is divided into two equal chambers by an internal diaphragm. One

chamber contains methane at a pressure of 500 bar and a temperature of
20◦ C, and the other chamber is evacuated. Suddenly, the diaphragm
bursts. Compute the final temperature and pressure of the gas in the tank
after sufficient time has passed for equilibrium to be attained. Assume that
there is no heat transfer between the tank and the gas and that methane
obeys the van der Waals equation of state. Data: C∗p = 35.56J/mol K

M. Hamsa Priya BT2061:Problems 16 / 51

 Real Gases

Problem 16

A tank containing carbon dioxide at 400 K and 50 bar is vented until the
temperature in the tank falls to 300 K. Assuming there is no heat transfer
between the gas and the tank, find the pressure in the tank at the end of
the venting process and the fraction of the initial mass of gas remaining in
the tank for each of the following cases. Assume carbon dioxide obeys
Clausius equation of state P(V − b) = RT with b = 0.0441m3 /kmol

M. Hamsa Priya BT2061:Problems 17 / 51

 Real Gases

Problem 17

One hundred cubic-meters of carbon dioxide initially at 150◦ C and 50 bar

is to be isothermally compressed in a frictionless piston and cylinder device
to a final pressure of 300 bar. Assume CO2 obeys corresponding state,
calculate a) the volume of the compressed gas; b) the workdone to
compress the gas; c) the heat flow on compression.

M. Hamsa Priya BT2061:Problems 18 / 51

 Real Gases

Problem 18

Ammonia is to be isothermally compressed in a specially designed flow

turbine from 1 bar and 100◦ C to 50 bar. If the compression is done
reversibly, compute the heat and work flows needed per mole of ammonia.
Assume the process is carried out at steady state condition and ammonia
obeys the principle of corresponding state.
Critical Properties: Tc = 405.6 K, Pc = 11.28 MPa,
Vc = 0.0724 m3 /kmol.

M. Hamsa Priya BT2061:Problems 19 / 51

 Real Gases

Problem 19

A tank is divided into two equal chambers by an internal diaphragm. One

chamber contains methane at a pressure of 500 bar and a temperature of
20◦ C, and the other chamber is evacuated. Suddenly, the diaphragm
bursts. Compute the final temperature and pressure of the gas in the tank
after sufficient time has passed for equilibrium to be attained. Assume
that there is no heat transfer between the tank and the gas and the
methane obeys the principle of corresponding states
Critical Properties: Tc = 190.6 K, Pc = 4.6 MPa, Vc = 0.099 m3 /kmol.

M. Hamsa Priya BT2061:Problems 20 / 51

 Real Gases

Problem 20

Steam at 20 bar and 300◦ C is to be continuously expanded to 1 bar.

Compute the final temperature, the entropy generated, the heat required,
and the work obtained per kilogram of steam if this expansion is done by
passing the steam through a well-designed , isothermal turbine. Will the
final state be a vapor, a liquid or a vapor-liquid mixture? If it is a
vapor-liquid mixture, determine the fraction of vapor and liquid content.

M. Hamsa Priya BT2061:Problems 21 / 51

 Real Gases

Problem 21

Evaluate the difference

   
∂U ∂U
−
∂T P ∂T V

for the ideal and van der Waals gases.

M. Hamsa Priya BT2061:Problems 22 / 51

 Real Gases

Problem 22
One of the beauties of thermodynamics is that it provides
interrelationships between various state variables and their derivatives so
that information from one set of experiments can be used to predict the
results of a completely different experiment. This is illustrated here.
a. Show that T2 ∂(V/T)
 
Cp =
µ ∂T P
Thus, if the Joule-Thomson Coefficient µ and the volumetric equation of
state (in analytic or tabular form) are known for a fluid, Cp , can be
computed. Alternatively, if Cp and µ are known, (∂(V/T)/∂T)P can be
calculated, or if Cp and (∂(V/T)/∂T)P are known, µ can be calculated.
b. Show that Z P,T2
T2 µCp
V(P, T2 ) = V(P, T1 ) + T2 dT
T1 P,T1 T2
so that if µ and Cp are known functions of temperature at pressure P, and
V is known at P and T1 , the specific volume at P and T2 can be
computed.
M. Hamsa Priya BT2061:Problems 23 / 51
 Real Gases

Problem 23
By measuring the temperature change and the specific volume change
accompanying a small pressure change in a reversible adiabatic process,
one can evaluate the derivative
 
∂T
∂P S

and the adiabatic compressibility

 
1 ∂V
κS = −
V ∂P S

Develop an expression for (∂T/∂P)S in terms of T, V, Cp , α and κT , and

show that
κS CV
=
κT Cp

M. Hamsa Priya BT2061:Problems 24 / 51

 Real Gases

Problem 24
The Clausius equation of state is
P(V − b) = RT
a. Show that for this volumetric equation of state
Cp (P, T) = Cv (P, T) + R
Cp (P, T) = C∗p (T)
and
Cv (V, T) = C∗v (T)
b. For a certain process the pressure of a gas must be reduced from an
initial pressure P1 to the final pressure P2 . The gas obeys the Clausius
equation of state, and the pressure reduction is to be accomplished either
by passing the gas through a flow constriction, such as pressue-reducing
valve, or by passing it through a small gas turbine (which we can assume
to be both reversible and adiabatic). Obtain expressions for the final gas
temperature in each of these cases in terms of the initial state and the
properties of the gas.
M. Hamsa Priya BT2061:Problems 25 / 51
 Real Gases

Problem 25

Derive the following Maxwell relations for open systems from the first
fundamental equation of thermodynamics
   
∂T ∂P
=−
∂V S,N ∂S V,N
   
∂T ∂G
=
∂N S,V ∂S V,N
   
∂P ∂G
=−
∂N S,V ∂V S,N

M. Hamsa Priya BT2061:Problems 26 / 51

 Single component VLE

Problem 26

The triple point of iodine, I2 , occurs at 112.9◦ C and 11.57 kPa. The heat
of fusion at the triple point is 15.27 kJ/mol, and the following vapor
pressure data are available for solid iodine:

Vapor pressure (kPa) 2.67 5.33 8.00

Temperature(◦ C) 84.7 97.5 105.4

Estimate the normal boiling temperature of molecular iodine.

M. Hamsa Priya BT2061:Problems 27 / 51

 Single component VLE

Problem 27
The following data are available for carbon tetrachloride:
Tc = 283.3◦ ; Pc = 4.56 MPa; Zc = 0.272
Vapor pressure (MPa) 0.5065 1.013 2.026
Temperature(◦ C) 141.7 178.0 222.0
a. Compute the heat of vaporization of carbon tetrachloride at 200◦ C
using only these data
b. Derive the following expression, which can be used to compute the heat
of vaporization from the principle of corresponding states:
" #
H − HIG H − HIG
  
∆vap H = Tc −
Tc sat.vap. Tc sat.liq.

c. Compute the heat of vaporization of carbon tetrachloride at 200◦ C

using the principle of corresponding states.
d. Comment on the reasons for the difference between the heats of
vaporization computed in parts (a) and (c)
M. Hamsa Priya BT2061:Problems 28 / 51
 Single component VLE

Problem 28

a. The heat of vaporization for the steam-water phase transition is 2255

kJ/kg at 100◦ C and 1 bar. Develop an expression for the change in the
boiling temperature of water with pressure.
b. Compute the freezing and boiling points of water in a region where the
mean atmospheric pressure is 84.6 kPa

M. Hamsa Priya BT2061:Problems 29 / 51

 Single component VLE

Problem 29

A well insulated gas cylinder, containing ethylene at 85 bar and 25◦ C, is

exhausted until the pressure drops to 10 bar. This process occurs fast
enough that no heat transfer occurs between the gas and the cylinder
walls, but not so rapidly as to produce large velocity or temperature
gradients within the cylinder.
a. Calculate the final temperature of the ethylene in the cylinder.
b. What fraction of the ethylene remaining in the cylinder is present as a
liquid?

M. Hamsa Priya BT2061:Problems 30 / 51

 Single component VLE

Problem 30

Calculate the fugacity of liquid water at 300◦ C and 25 MPa.

M. Hamsa Priya BT2061:Problems 31 / 51

 Single component VLE

Problem 31

The critical temperature of benzene is 289◦ C and its critical pressure is

4.89 MPa. At 220◦ C its vapor pressure is 1.91 MPa.
a. Calculate the fugacity of liquid benzene in equilibrium with its pure
vapor at 220◦ C
b. Repeat the calculation for the case in which liquid benzene is under an
atmosphere of hydrogen such that the total pressure is 13.61 MPa. The
average density of liquid benzene at these condition is 0.63 g/cc, and you
can assume that hydrogen is insoluble in benzene at this temperature. The
molecular weight of benzene is 78.02.

M. Hamsa Priya BT2061:Problems 32 / 51

 Binary Systems

Problem 32

The enthalpies of a binary mixture (in J/mol) at 298.15 K are given by

Hmix − [x1 H1 + x2 H2 ] = x1 x2 {1418 − 482.4(1 − 2x1 ) + 187.4(1 − 2x1 )3 } ,

where xi is the mole fraction of component i.

a. Develop expressions for (H1 − H1 ) and (H2 − H2 )
b. Compute values for (H1 − H1 ) and (H2 − H2 ) at x1 = 0.5.
c. When one mole of the binary mixture of composition x1 = 0.25, is to
be mixed with a mixture of composition x1 = 0.75 at 298.15 K, how much
heat must be added or removed for the process to be isothermal?

M. Hamsa Priya BT2061:Problems 33 / 51

 Binary Systems

Problem 33

Laboratory alcohol is usually not pure alcohol, but a mixture of alcohol

and water. 2 L of laboratory alcohol containing 96% alcohol (A) has to be
diluted to a solution containing 56% alcohol for an experiment. All
percentages are on weight basis. Calculate the volume of water required
for the dilution, and the volume of the diluted alcohol solution.
Data: The partial specific volumes are as follows
In 96% alcohol solution, VW = 0.816 × 10−3 m3 /kg,
VA = 1.273 × 10−3 m3 /kg
In 56% alcohol solution, VW = 0.953 × 10−3 m3 /kg,
VA = 1.243 × 10−3 m3 /kg
The density of water may be taken as 0.997 × 103 kg/m3

M. Hamsa Priya BT2061:Problems 34 / 51

 Binary Systems

Problem 34
a. Show that the minimum amount of work, Wsmin , necessary to separate
1 mole of a binary mixture into its pure components at constant
temperature and pressure is
f1 (T, P) f2 (T, P)
Wsmin = x1 RT ln + x2 RT ln
f 1 (T, P, x1 ) f 2 (T, P, x2 )
b. Show that this expression reduces to

Wsmin = −x1 RT ln x1 − x2 RT ln x2

for (i) an ideal liquid mixture and (ii) a gaseous mixture for which the
Lewis-Randall rule is obeyed.
c. Calculate the minimum amount of work needed to separate a 50/50
mixture of two isomers at 300 K and a pressure of 1 bar into its pure
components at the same temperature and pressure. Explicitly state and
justify all assumptions.
M. Hamsa Priya BT2061:Problems 35 / 51
 Binary Systems

Problem 35
The excess Gibbs energies for liquid argon-methane mixtures have been
measured at several temperatures. The results are
Gex
= xAr (1 − xAr ){A − B(1 − 2xAr )} ,
RT
where numerical values for the parameters are given as
T(K) A B
109.0 0.3024 -0.01453
112.0 0.2929 -0.01169
115.75 0.2792 +0.05115
Compute the following a. The activity coefficients of argon and methane
at 112.0 K and xAr = 0.5
b. The molar isothermal enthalpy change on producing an xAr = 0.5
mixture from its pure components at 112.0 K
c. The molar isothermal entropy change on producing an xAr = 0.5
mixture from its pure components at 112.0 K
M. Hamsa Priya BT2061:Problems 36 / 51
 Binary Systems

Problem 36

Air contains approximately 21 mol% oxygen an 79 mol% nitrogen. An

engineer claims to have developed a continuous process in which air is first
compressed to 2 bar and 25◦ C, and then isothermally expanded to
atmospheric pressure through a secret device that has no moving parts and
results in two gas streams. The first stream is said to contain 99 mol%
oxygen, and the second stream contains only 5 mol% oxygen. Prove
whether such a device is thermodynamically possible.

M. Hamsa Priya BT2061:Problems 37 / 51

 Binary Systems

Problem 37

The heat of mixing data for n-octanol and n-decane liquid mixture at
atmospheric pressure is approximately fit by

∆mix H = x1 x2 (A + B(x1 − x2 )) J/mol (1)

where, A = −12, 974 + 51.505 T and B = +8782.8 − 34.129 T with T in

K and x1 being the n-octanol mole fraction.
a. Compute the difference between the partial molar and pure-component
enthalpies of n-octanol and n-decane at x1 = 0.5 and T = 300 K.
b. An x1 = 0.2 solution and an x1 = 0.9 solution are to flow continuously
into an isothermal mixer in the mole ratio 2:1 at 300 K. Will heat have to
be added or removed to keep the temperature of the solution leaving the
mixer at 300 K? What will be the heat flow per mole of solution leaving
the mixer?

M. Hamsa Priya BT2061:Problems 38 / 51

 Binary VLE

Problem 38

Using the following data, estimate the total pressure and composition of
the vapor in equilibrium with a 20 mol % ethanol (1) solution in water (2)
at 78.15◦ C.
Data (at 78.15◦ C): Vapor pressure of ethanol (1) = 1.006 bar; Vapor
pressure of water (2) = 0.439 bar; limx1 →0 γ1 = γ1∞ = 1.6931;
limx2 →0 γ2 = γ2∞ = 1.9523

M. Hamsa Priya BT2061:Problems 39 / 51

 Binary VLE

Problem 39

Based on vapor-liquid equilibrium data, some authors have claimed that

the benzene (1) - cyclohexane (2) mixture is described by

G ex = Ax1 x2 ,

where A (J/mol) = 3750 − 8T for T in degrees K.

a. Determine the enthalpy and entropy changes on mixing when 1 mole of
benzene and 2 moles of cyclohexane are mixed at T = 300 K and constant
pressure.
b. Given the following vapor pressure data at T = 320 K, Pvap1 = 0.3203
bar and Pvap
2 = 0.3218 bar, determine the bubble point pressure of the
liquid in part (a) at T = 320 K, and the composition of the vapor in
equilibrium with that liquid.

M. Hamsa Priya BT2061:Problems 40 / 51

 Binary VLE

Problem 40

A binary mixture of components 1 and 2 is in vapor-liquid equilibrium.

a. At 90◦ C and 1.8505 bar pressure, a vapor of composition y1 = 0.3767
coexists with a liquid of composition x1 = 0.4. Use these data to
determine the van Laar parameters for this mixture.
b. A equimolar mixture of species 1 and 2 at initially very low pressure is
compressed at a constant temperature of 90◦ C. At what pressure does the
first drop of liquid form, and what is its composition? At what pressure
does the last bubble of vapor disappear, and what was its composition?
Data: The vapor pressures of the components are given by
Bi
log10 Pivap = Ai −
T
for pressure in bar and T in K, where A1 = 4.125, B1 = 1500, A2 = 5.000,
and B2 = 1750.

M. Hamsa Priya BT2061:Problems 41 / 51

 Binary VLE

Problem 41

The bubble point of a liquid mixture of an alcohol and water containing

2.0 mol % alcohol is 90◦ C at 1.013 bar. The vapor pressure of pure water
is 0.7733 bar and that of the alcohol is 0.4 bar at this temperature.
a. Assuming that the activity coefficient of water is unity (since its
concentration is 98 mol %). What is the composition of the vapor in
equilibrium with the 2 mol % solution? What is the activity coefficient of
the alcohol in this solution?
b. At 90◦ C, the maximum amount of alcohol that can be dissolved in
water is 2.0 mol %. When large amounts are present, a second liquid
phase forms that contains 65.0 mol % alcohol. What are the activity
coefficients of the alcohol and the water in this second liquid phase?

M. Hamsa Priya BT2061:Problems 42 / 51

 Binary VLE

Problem 42

The bubble point of a liquid mixture of n-butanol and water containing 4.0
mol % butanol is 92.7◦ C at 1.013 bar. At 92.7◦ C the vapor pressure of
pure water is 0.784 bar and that of pure n-butanol is 0.427 bar. (5 marks)
a. Assuming the activity coefficient of water in the 4.0 mol % butanol
solution is about 1, what is the composition of the vapor in equilibrium
with the 4.0 mol % butanol-water mixture, and what is the activity
coefficient of n-butanol?
b. At 92.7◦ C, the maximum amount of n-butanol that can be dissolved in
water is 4.0 mol %. When larger amounts of n-butanol are present, a
second liquid phase, containing 40.0 mol % n-butanol, appears. What are
the activity coefficients for n-butanol and water in this second liquid phase?
c. If the two coexisting liquids in part (b) are kept at 92.7◦ C, what will be
the pressure when the first bubble of vapor is formed?

M. Hamsa Priya BT2061:Problems 43 / 51

 Solubility

Problem 43

Here we want to estimate the solubility of gaseous nitrogen in liquid

carbon tetrachloride at 25◦ and a partial pressure of nitrogen of 1 bar. The
(hypothetical) liquid nitrogen fugacity at 25◦ C is 1000 bar.
a. Calculate the mole fraction of nitrogen present in the liquid CCl4 at
equilibrium if the two species form an ideal solution.
b. From regular solution theory it is estimated that

ln γN2 = 0.526(1 − xN2 )2

What is the equilibrium mole fraction of nitrogen in CCl4 under these

circumstances? What is the Henry’s law constant for this system, if the
excess volume for this system is zero?

M. Hamsa Priya BT2061:Problems 44 / 51

 Solubility

Problem 44

Nitrofurantoin is an antibiotic that is used to eliminate bacteria that cause

urinary tract infections. The following data have been reported for its
solubility in water

T(◦ C) 24 30 37 45
xN × 106 6.01 8.57 13.16 18.99

Estimate the apparent heat of fusion of nitrofurantoin.

M. Hamsa Priya BT2061:Problems 45 / 51

 Solubility

Problem 45

At 25◦ C a saturated aqueous solution contains 0.171 M of L-leucine, while

a saturated solution in ethanol contains only 1.28 × 10−3 M of this amino
acid. What is the ratio of the activity coefficients of L-leucine in these two
solutions, and what is the Gibbs energy of transfer of L-leucine from water
to ethanol?

M. Hamsa Priya BT2061:Problems 46 / 51

 Solubility

Problem 46

The following data have been reported for the osmotic pressure of
α-chymotrpsin in water at pH = 8.0 in an 0.01 M potassium sulfate
solution at 25◦ C.

Cs (g/L) 0.901 1.841 4.070 5.558 7.211 9.298

Π (Pa) 58.7 121.2 271.3 376.9 476.7 615.0

Use these data to determine the molecular weight of α-chymotrpsin and

the value of its osmotic second virial coefficient, B2 , at these conditions.

M. Hamsa Priya BT2061:Problems 47 / 51

 Biochemical Reactions

Problem 47

Glucagon is a 29 amino peptide hormone of the pancreas. At pH = 10.6 it

is known that glucagon can associate or trimerize, and the following
standard-state (ideal 1-molal solution at 25◦ C) information is availalbe:
K 1
G
G3
3
∆rxn G ◦ = -30.6 kJ/mol; ∆rxn H ◦ = -131 kJ/mol and ∆rxn Cp◦ = -1.8
kJ/mol K
If the initial concentration of glucagon is 0.01 M (which is sufficiently low
for the solution to be considered ideal), what is the fraction of glucagon
trimerized at 25◦ C and at 50◦ C?

M. Hamsa Priya BT2061:Problems 48 / 51

 Biochemical Reactions

Problem 48

G-actin is a globular dimer of actin, a cytoskeleton protein. In solutions at

pH = 7.5, the following data are available for the unfolding of G-actin at
25◦ C:
∆unf G = 27 kJ/mol; ∆unf H = 197 kJ/mol and ∆unf Cp = 27 J/mol K.
Determine the melting temperature of the protein i.e., the temperature at
which half of the G-actin is unfolded.

M. Hamsa Priya BT2061:Problems 49 / 51

 Biochemical Reactions

Problem 49

The proteolytic enzyme α-chymotrpsin is known to dimerize. The

following data are available for this reaction at 25◦ C and pH = 7.8.

∆rxn G ◦ = -19.6 kJ/mol and ∆rxn S ◦ = -430.7 J/mol K

based on ideal 1 M standard states

a. Determine the equilibrium constant of this reaction at 37◦ C.
b. If the initial concentration of α-chymotrypsin is 0.001 M, determine the
fraction that is dimerized at 37◦ C.

M. Hamsa Priya BT2061:Problems 50 / 51

 Biochemical Reactions

Problem 50

Use the following information to determine the standard Gibbs free energy
change of ATP hydrolysis

Glucose + ATP → Glucose − 6 − Phosphate + ADP ∆G◦ = −16.7 kJ/mol

Glucose − 6 − Phosphate → Glucose + Pi ∆G◦ = −13.8 kJ/mol

If the cellular concentration of each species is 10 mM, what is the
corresponding Gibbs free energy change?

M. Hamsa Priya BT2061:Problems 51 / 51