MINISTRY OF HEALTH OF UKRAINE

BOGOMOLETS NATIONAL MEDICAL UNIVERSITY

Department of Medical Biochemistry and Molecular Biology

METODICAL INSTRACTIONS
FOR INDEPENDENT WORK OF STUDENTS
IN PREPARATION FOR A PRACTICAL (SEMINAR) LESSON

Academic Medical Chemistry

discipline

Module 1 "Fundamentals of Medical Chemistry"

Semantic “Heterogeneous equilibrium in biological liquids”
module 2
Topic 7 Chemical thermodynamics and bioenergetics.
For the First Year Foreign Students
Training of specialists of the second (master's) level of
higher education
Branch of 22 “Healthcare”
knowledge
Speciality 221 “Medicine”
Duration of the 3 hours
practical lesson
Worked out by: associate professor Nataliya Tereshchenko,
professor Valentyna Slipchuk,
associate professor Galina Zaitseva

2021 – 2022 academic year

Topic 7 Chemical thermodynamics and bioenergetics.
Lesson purposes:
 to form knowledge about the Chemical thermodynamics and bioenergetics;

Actual aims and abilities:

 to explain the sense of terms: thermodynamic system, function of condition,
heat, work, internal energy, enthalpy;
 To formulate the The Laws of Thermodynamics;
 To formulate Hess law and its consequences and to apply them to simple
calculations;
 To use thermochemical calculations for characterizing the biochemical processes
energy;

Content of the lesson

Thermodynamics is defined as the branch of science that deals with the relationship
between heat and other forms of energy, such as work. It is frequently summarized as
three laws that describe restrictions on how different forms of energy can be
interconverted. Chemical thermodynamics is the portion of thermodynamics that
pertains to chemical reactions.
The Laws of Thermodynamics
First law: Energy is conserved; it can be neither created nor destroyed.
Second law: In an isolated system, natural processes are spontaneous when
they lead to an increase in disorder, or entropy.
Third law: The entropy of a perfect crystal is zero when the temperature of
the crystal is equal to absolute zero (0 K).
There have been many attempts to build a device that violates the laws of
thermodynamics. All have failed. Thermodynamics is one of the few areas of science
in which there are no exceptions.
Practice Problem 1
Which of the following processes are run at constant volume and which are run at
constant pressure?
(a) an acid-base titration
(b) decomposing CaCo3 by heating limestone in a crucible with a bunsen burner
(c) the reaction bewteen zinc metal and an aqueous solution of Cu2+ ion to form
copper metal and Zn2+ ions
(d) measuring the calories in a 1-oz. serving of breakfast cereal by burning the cereal
in a bomb calorimeter

Answer
Processes (a), (b), and (c) are all run under conditions of constant pressure. Only (d)
is run at constant volume.
Many chemical and physical processes are reversible and yet tend to proceed
in a direction in which they are said to be spontaneous. This raises an obvious
question: What makes a reaction spontaneous? What drives the reaction in one
direction and not the other?
So many spontaneous reactions are exothermic that it is tempting to assume that one
of the driving forces that determines whether a reaction is spontaneous is a tendency
 to give off energy. The following are all examples of spontaneous chemical reactions
that are exothermic.
2 Al(s) + 3 Br2(l) 2 AlBr3(s) Ho = -511 kJ/mol AlBr3
2 H2(g) + O2(g) 2 H2O(g) Ho = -241.82 kJ/mol H2O
P4(s) + 5 O2(g) P4O10(s) Ho = -2984 kJ/mol P4O10
There are also spontaneous reactions, however, that absorb energy from their
surroundings. At 100oC, water boils spontaneously even though the reaction is
endothermic.
H2O(l) H2O(g) Ho = 40.88 kJ/mol
Ammonium nitrate dissolves spontaneously in water, even though energy is absorbed
when this reaction takes place.
H2O
NH4NO3(s) NH4+(aq) + NO3-(aq) Ho = 28.05 kJ/mol
Thus, the tendency of a spontaneous reaction to give off energy can't be the only
driving force behind a chemical reaction. There must be another factor that helps
determine whether a reaction is spontaneous. This factor, known as entropy, is a
measure of the disorder of the system.
Entropy and the Second Law of Thermodynamics
The second law of thermodynamics describes the relationship between entropy and
the spontaneity of natural processes.
Second Law: In an isolated system, natural processes are spontaneous when they
lead to an increase in disorder, or entropy.
This statement is restricted to isolated systems to avoid having to worry about
whether the reaction is exothermic or endothermic. By definition, neither heat nor
work can be transferred between an isolated system and its surroundings.
We can apply the second law of thermodynamics to chemical reactions by noting that
the entropy of a system is a state function that is directly proportional to the disorder
of the system.
Ssys > 0 implies that the system becomes more disordered during the reaction.
Ssys < 0 implies that the system becomes less disordered during the reaction.
For an isolated system, any process that leads to an increase in the disorder of the
system will be spontaneous. The following generalizations can help us decide when a
chemical reaction leads to an increase in the disorder of the system.
 Solids have a much more regular structure than liquids. Liquids are therefore
more disordered than solids.
 The particles in a gas are in a state of constant, random motion. Gases are
therefore more disordered than the corresponding liquids.
 Any process that increases the number of particles in the system increases the
amount of disorder.
Practice Problem 2:
Which of the following processes will lead to an increase in the entropy of the system?
(a) N2(g) + 3H2 (g) 2 NH3(g)
(b) H2O(l) H2O(g)
(c) CaCO3(s) CaO(s) + CO2(g)
(d) NH4NO3(s) + H2O(l) NH4+ (aq) + NO3- (aq)
Answer
(a) Because the total number of molecules decreases in this reaction, the system
becomes more ordered. The entropy of the system therefore decreases.
(b) Gases are more disordered than the corresponding liquids, so the entropy of the
system increases.
(c) Reactions in which a compound decomposes into two products lead to an increase
in entropy because the system becomes more disordered. The increase in entropy in
this reaction is even larger because the starting material is a solid and one of the
products is a gas.
(d) The NH4+ and NO3- ions are free to move in a random fashion through the
aqueous solution, whereas these ions are locked into position in the crystal. As a
result, the entropy of the system increases in this reaction.
The sign of H for a chemical reaction affects the direction in which the reaction
occurs.
Spontaneous reactions often, but not always, give off energy.
The sign of S for a reaction can also determine the direction of the reaction.
In an isolated system, chemical reactions occur in the direction that leads to an
increase in the disorder of the system.
In order to decide whether a reaction is spontaneous, it is therefore important to
consider the effect of changes in both enthalpy and entropy that occur during the
reaction.

Practice Problem 3:
Use the Lewis structures of NO2 and N2O4 and the stoichiometry of the following
reaction to decide whether H and S favor the reactants or products of this reaction:
2 NO2(g) N2O4(g)
Answer
H for this reaction favors the products. S for this reaction favors the reactants.
Solution
NO2 has an unpaired electron in its Lewis structure:

When two NO2 molecules collide in the proper orientation, a covalent bond can form
between the nbitrogen atoms to produce the dimer, N2O4:
Because it forms a new bond, this reaction should be exothermic. H for this reaction
therefore favors the products. The reaction leads to a decrease in the entropy of the
system because the system becomes less disordered when two molecules come
together to form a larger molecule S for this reaction therefore favors the reactants.
The Third Law of Thermodynamics
The third law of thermodynamics defines absolute zero on the entropy scale.
Third law: The entropy of a perfect crystal is zero when the temperature of the
crystal is equal to absolute zero (0 K).
Standard-State Entropies of Reaction
S = Sf - Si
S for a chemical reaction is therefore equal to the difference between the sum of the
entropies of the reactants and the products of the reaction.
S = S(products) - S(reactants)
When this difference is measured under standard-state conditions, the result is the
standard-state entropy of reaction, So.
So = So(products) - So(reactants)
By convention, the standard state for thermodynamic measurements is characterized
by the following conditions.
Standard-state conditions:
All solutions have concentrations of 1 M.
All gases have partial pressures of 0.1 MPa (0.9869 atm)
Although standard-state entropies can be measured at any temperature, they are often
measured at 25oC.

Practice Problem 4:
Calculate the standard-state entropy of reaction for the following reactions and
explain the sign of S° for each reaction.
(a) Hg(l) Hg(g)
(b) 2NO2(g) N2O4(g)
(c) N2(g) + O2(g) 2NO(g)
Answer
(a) 98.94 J/K, the sign of So is positive.
(b) -175.83 J/K, the sign of So is negative.
(c) 24.77 J/K, the sign of So for this reaction is small but positive.
Solution
(a) Using a standard-state entropy data table, we find the following information:
Compound S°(J/mol-K)
Hg(l) 76.02
Hg(s) 174.96
The balanced equation states that 1 mole of mercury vapor is produced for each mole
of liquid mercury that boils. The standard-state entropy of reaction is therefore
calculated as follows:
So = So(products) - So(reactants)
= [1 mol Hg(g) x 174.96 J/mol-K] - [1 mol Hg(l) x 76.02 J/mol-K]
= 98.94 J/K
The sign of So is positive because this process transforms a liquid into a gas, which
is inherently more disordered.
(b) Using a standard-state entropy data table, we find the following information:
Compound S°(J/mol-K)
NO2(g) 240.06
N2O4(g) 304.29
In this equation, 1 mole of N2O4 is formed for every mole of NO2 consumed, and the
value of So is calculated as follows:
So = So(products) - So(reactants)
= [1 mol N2O4(g) x 304.29 J/mol-K] - [2 mol NO2(l) x 240.06 J/mol-K]
= -175.83 J/K
The sign of So is negative because two molecules combine in this reaction to form a
larger, more ordered product.
(c) Using a standard-state entropy data table, we find the following information:
Compound S°(J/mol-K)
NO(g) 210.76
N2(g) 191.61
O2(g) 205.14
The balanced equation for this reaction indicates that 2 mole of NO are produced
when 1 mole of N2 reacts with 1 mole of O2 . Thus, the standard-state entropy of
reaction is calculated as follows:
So = So(products) - So(reactants)
= [2 mol NO x 210.76 J/mol-K] - [1 mol N2 x 191/61 J/mol-K + 1 mol O2 x
205.14 J/mol-K]
= 24.77 J/K
So for this reaction is small but positive because the product of the reaction (NO) is
slightly more disordered that the reactants ( N2 and O2).
Driving Forces and Gibbs Free Energy
Some reactions are spontaneous because they give off energy in the form of heat ( H
< 0). Others are spontaneous because they lead to an increase in the disorder of the
system ( S > 0). Calculations of H and S can be used to probe the driving force
behind a particular reaction.
Practice Problem 5:
Calculate H° and S° for the following reaction and decide in which direction each
of these factors will drive the reaction.
N2(g) + 3 H2(g) 2 NH3(g)
Answer
Ho = -92.22 kJ
So = -198.75 J/K
Solution
Using a standard-state enthalpy of formation and absolute entropy data table, we find
the following information:
Compound Hfo(kJ/mol) S°(J/mol-K)
N2(g) 0 191.61
H2(g) 0 130.68
NH3(g) -46.11 192.45
The reaction is exothermic ( H° < 0), which means that the enthalpy of reaction
favors the products of the reaction:
Ho = Hfo(products) - Hfo(reactants)
= [2 mol NH3 x 46.11 kJ/mol] - [1 mol N2 x 0 kJ/mol + 3 mol H2 x 0 kJ/mol]
= -92.22 kJ
The entropy of reaction is unfavorable, however, because there is a significant
increase in the order of the system, when N2 and H2 combine to form NH3.
 So = So(products) - So(reactants)
= [2 mol NH3 x 192.45 J/mol-K] - [1 mol N2 x 191.61 J/mol-K + 3 mol H2 x
130.68 J/mol-K]
= -198.75 J/K
Reactions are classified as either exothermic ( H < 0) or endothermic ( H > 0) on
the basis of whether they give off or absorb heat. Reactions can also be classified as
exergonic ( G < 0) or endergonic ( G > 0) on the basis of whether the free energy
of the system decreases or increases during the reaction.
Practice Problem 6:
Calculate H° and S° for the following reaction:
NH4NO3(s) + H2O(l) NH4+ (aq) + NO3- (aq)
Use the results of this calculation to determine the value of Go for this reaction at 25o
C, and explain why NH4NO3 spontaneously dissolves is water at room temperature.
Answer
Ho = 28.05 kJ
So = 108.7 J/K
Go = -4.4 kJ
Solution
Using a standard-state enthalpy of formation and absolute entropy data table, we find
the following information:
Compound Hfo(kJ/mol) S°(J/mol-K)
NH4NO3(s) -365.56 151.08
NH4+ (aq) -132.51 113.4
NO3- (aq) -205.0 146.4
This reaction is endothermic, and the enthalpy of reaction is therefore unfavorable:
Ho = Hfo(products) - Hfo(reactants)
= [1 mol NH4 x 132.51 kJ/mol + 1 mol NO3- x -205.0 kJ/mol] - [1 mol NH4NO3
x -365.56 kJ/mol]
= 28.05 kJ
The reaction leads to a significant increase in the disorder of the system, however, and
is therefore favored by the entropy of reaction:
So = So(products) - So(reactants)
= [1 mol NH4 x 113.4 J/mol-K + 1 mol NO3- x 146.4 J/mol-K] - [1 mol NH4NO3
x 151.08 J/mol-K]
= 108.7 J/K
To decide whether NH4NO3 should dissolve in water at 25o C we have to compare the
Ho and T So to see which is larger. Before we can do this, we have to convert the
temperature from oC to kelvin:
TK = 25o C + 273.15 = 298.15 K
We also have to recognize that the units of Ho for this reaction are kilojoules and
the units of So are joules per kelvin. At some point in this calculation, we therefore
have to convert these quantites to a consistent set of untis. Perhaps the easiest way of
doing this is to convert Ho to joules. We then multiply the entropy term by the
absolute temperature and subtract this quantity from the enthalpy term:
Go = Ho - T So
= 28,050 J - (298.15 K x 108.7 J/K)
= 28,050 J - 32,410 J
= -4360 J
At 25o C, the standard-state free energy for this reaction is negative because the
entropy term at this temperature is larger that the enthalpy term:
 Go = -4.4 kJ
The reaction is therefore spontaneous at room temperature.
Practice Problem 7:
Use the values of H° and S° calculated in Practice Problem 5 to predict whether
the following reaction is spontaneous at 25°C:
N2(g) + 3 H2(g) 2 NH3(g)
Answer
Go = -32.96 kJ, the reaction should be spontaneous at 25°C.
Solution
According to Practie Problem 5, this reaction is favored by enthalpy but not by
entropy:
H° = -92.22 kJ (favorable)
S° = -198.75 J/K (unfavorable)
Before we can compare these terms to see which is larger, we have to incorporate inot
our calculation the tmeperature at which the reaction is run:
TK = 25o C + 273.15 = 298.15 K
We then multiply the entropy of reaction by the absolute temperature and subtract the
T So term from the Ho term:
Go = Ho - T So
= -92,220 J - (298.15 K x -198.75 J/K)
= -92,220 J + 59,260 J
= -32,960 J
Go = -32.96 kJ
According to this calculation, the reaction should be spontaneous at 25°C.
Realization

Examples for test:

1. Exothermic process is a process in which Delta H is:
a) ΔH=0 b) ΔH>0 c) ΔH<0.
2. The Earth is:
a. an open system
b. a closed system
c. an isolated system
3. The condition of thermodynamics equilibrium of the closed system at ΔV=0, ΔT=0:
а)ΔF=0 b) ΔG=0 c) ΔF>0 d) ΔH=0
f)ΔF<0
4. The change of entalpy of the system describes by:
а)Q= ΔU+А b) ΔG=ΔH- TΔS c) ΔH=ΔU+рΔV d) ΔF=ΔU-
TΔS
5. What parameter of the system is the state function?
а) Р b) Н c) V
6. The change of Gibbs free energy describes by:
а) ΔF=ΔU-TΔS b)ΔG=ΔH- TΔS c) ΔH=ΔU+рΔ V d)
Q= ΔU+А
7. The change of entropy of the following reaction COCl2=CO + Cl2 is:
а) ΔS>0 b) ΔS=0 c) ΔS<0.
Recommended Books
Basic literature:
1. Medical chemistry: textbook / V.O. Kalibabchuk, V.I. Halynska, L.I. ,
Hryshchenko et al.; edited by V.O. Kalibabchuk. – 7th edition, corrected. – Kyiv:
AUS Medicine Publishing, 2020. p.24-39.
2. Medical chemistry: textbook / V.O. Kalibabchuk, V.I. Halynska, L.I.
Hryshchenko et al.; edited by V.O. Kalibabchuk. – 6th edition, corrected. – Kyiv:
AUS Medicine Publishing, 2018. p.
Auxiliary:
1. General and Inorganic Chemistry: textbook/ V.O. Kalibabchuk, V.V. Ohurtsov, V.I.
Halynska et al.; edited by V.O. Kalibabchuk.-Kyiv: AUS Medicine Publishing,
2019. – 456p.
2. C. E. Housecroft. Chemistry: an introduction to organic, inorganic, and physical
chemistry, 4th edition. – Pearson – 2010. – 1517 p.
3. John W. Moore, Conrad L. Stanitski, Peter C. Jurs Chemistry: the molecular
science. first ed. / Thomson learning, Inc.: – USA. – 2002. - 1017 p.
Information resources
1. Official site of Bogomolets NMU http://nmuofficial.com/en/
2.Training platform of Bogomolets NMU
https://likar.nmuofficial.com/md/course/view.php?id=6842