Lecture 3.

Chemical
thermodynamics
 Plan of the lecture
1. The First Law of Thermodynamics
A. A system, surroundings, work, heat
B. Terms and concepts
C. Units of Energy

2. The first law of thermodynamics

A. Internal energy
B. Endothermic and exothermic processes
C. Enthalpy
D. Hess’ law and standard enthalpy of formation

3. The second law of thermodynamics and

entropy

4. Gibbs free energy changes

All chemical reactions are accompanied by transformation of chemical
energy to other forms of energy – thermal, electrical, mechanical, etc.

Thermodynamics – is a branch of physical science that studies all forms of

energy and their mutual transformation.

Bioenergetics – is a field of thermodynamics that deals with biosystems.

Thermochemistry – studies the effects of thermal and chemical processes.

Thermochemistry is very important for medicine because it helps:

1) To generate scientific representation of the energy balance of a living

organism;
2) To establish connection between the caloric content of food and energy
expenses of the organism;
3) To determine possibility of separate reactions of the human body.
Terms and concepts

A system is defined as the matter within a defined region of space. The

matter in the rest of the universe is called the surroundings.
There are several types of systems:
1) An open system is one where both matter and energy can freely cross
from the system to the surroundings and back (an open flask).
2) A closed system is one where energy can cross the boundary, but
matter cannot (a sealed flask).
3) An isolated system is one where neither matter nor energy can cross
between the system and the surroundings .
The universe itself is an isolated system (as there are no surroundings to
exchange matter or energy with).

a. Open system b. Closed system c. Isolated system

Terms and concepts

Work - is the organized form of Heat - is the transfer of energy by a

energy transfer associated with the disordered or chaotic motion. Heat is
motion of microscopic particles as a transferred to or from a system when
whole (in a certain direction). there is a temperature difference
Work is done when something is between the system and the
moved against an opposing force. surroundings. (Temperature determines
the direction of that heat flow, from hot
Consider lifting an object - work is to cold).
done during the process as the object
is moved upwards against the
opposing force of its own weight.
Energy is required to carry out the
process.
Terms and concepts

Thermodynamic parameters:
extensive and intensive.
If the system changes its parameters, then it
takes a thermodynamic process.
Extensive: These variables or properties
depend on the amount of substance present
(e.g. mass or volume). The parameters are
summed up.
Intensive: These variables or properties DO
NOT depend on the amount of substance (e.g.
density, pressure, and temperature). The
parameters are averaged.
Terms and concepts

Types of processes

Any change of parameter in the system called

the thermodynamic process.
Isotermal process is a process in which
temperature remains constant (T=const).
Isobaric process is a process in which
preassure remains constant (p=const).
Isochoric process is a process in which
volume remains constant (V=const).
Adiabatic process is a process with no heat
transfer into or out of the system (Q=0).
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Terms and concepts

Reversible process is a process that can be reversed by

means of infinitesimal changes in some property of
the system without loss or dissipation of energy, and
can be reversed without causing change in the
surroundings.

Irreversible process is a process in which the system

and its surroundings cannot be simultaneously
returned to their initial states after the process has
been completed.

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Terms and concepts

Main objective of thermodynamics is

to be able to determine if a reaction will
occur when reactants are brought
together under certain conditions.

Spontaneous process is a process, which under

particular conditions occurs by itself without
extraneous source of energy.

Non-spontaneous process is a process, which under

particular conditions cannot occur by itself without
extraneous source of energy.
Terms and concepts

Spontaneous Processes

Processes that are spontaneous at one temperature

may be nonspontaneous at other temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.
 Learning Check
1. When no heat energy is allowed to enter
or leave the system, it is called:

A. Irreversible process
B. Reversible process
C. Adiabatic process
D. Isothermal process
Terms and concepts

State functions are properties that are determined by

the state of the system, regardless of how that condition
was achieved.
energy, pressure, volume, temperature

Potential energy of hiker 1

and hiker 2 is the same even
though they took different
paths.
Terms and concepts

Thermodynamic functions of condition -

functions depending on the state of the
system and not by the way and the manner
in which this state is reached. This is:

internal energy (U),

enthalpy (H),
entropy (S)
Gibbs free energy (G)
Helmholtz free energy (F)
Units of Energy
SI Unit for energy is the Joule, J:
2 -2
Ek = 1 kg m s = 1 J
establish the equation

Sometimes the calorie is used instead of the Joule:

1 cal = 4.184 J (exactly)
or
1 J = 0.239 cal

A nutritional Calorie:
1 Cal = 1000 cal = 1 kcal
The first law of thermodynamics

The First Law of Thermodynamics states that the total energy

of a system and its surroundings is constant.
 
Euniv = Esys + Esurr = 0

In other words, the energy content of the universe is constant;

energy can be transformed, i.e. changed from one form to another,
but cannot be created nor destroyed.
Energy can take different forms, however.
Solar Optical → Electrical
Nuclear Nuclear → Heat, Kinetic,
Optical
Food Chemical → Heat, Kinetic
Photosynthesis Optical → Chemical
The first law of thermodynamics

Generally in chemistry is not required to know the

absolute value of internal energy.
Most important to know value of change of internal
energy in chemical processes.
If the internal energy of a system in the initial state is
U1 and in the final state U2, then the change of
internal energy ΔU may be given by:
ΔU = U2 − U1
Similarly in chemical reaction, Ur is the internal
energy of the reactants and Up is the internal energy
of products, then the change of internal energy ΔU:
ΔU = Up − Ur
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The first law of thermodynamics

The internal energy of system (U) encompasses

many different things, including:

1) the kinetic energy associated with the motions

of the atoms,
2) the potential energy stored in the chemical
bonds of the molecules,
3) the gravitational energy of the system.

It is nearly impossible to sum all of these

contributions up to determine the absolute energy of
the system.
 1st law of thermodynamics
 Law of Conservation of Energy

Energy can neither be created nor destroyed;

energy can only be transferred or changed
from one form to another.

Energy equation for stationary closed system:

∆U = Q − W
where ΔU – the change of internal energy;
Q – the heat transferred to the system;
W – the work done by the system.
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1st law of thermodynamics
Endothermic and exothermic processes

Since heat transfer is an important component of many

processes special words have been created to describe the
direction of heat flow in a process. Primarily we will use
these terms when referring to chemical reactions.

Exothermic Reactions
• Q > 0;
• reaction releases heat (heat leaves the system)
• heat is a product of the reaction .

Endothermic Reactions
• Q < 0;
• reaction absorbs heat (heat enters the system)
• heat is a reactant in the reaction
 Reaction enthalpy

Some reactions give off so much energy (primarily as heat) that

Unit:
they are explosive, other reactions give off only a little bit of
kJ/mol heat, still other reactions don’t take place unless we add heat
from the surroundings. It’s very useful information to know how
much heat a reaction will give off/absorb. This quantity is called
reaction enthalpy.

Enthalpy is a state function (doesn’t depend upon the path of the

reaction only the initial and final states). Therefore, we can
determine the enthalpy change, ΔH, of a chemical reaction by
subtracting the enthalpy of the reactants from the enthalpy of the
products:
 
ΔHrxn = ΣHproducts - ΣHreactants
 
The importance of this property will become evident when we
discuss Hess’ Law and standard enthalpy of formation.
Enthalpy

Enthalpy is a measure of the total energy of a thermodynamic

system that is available for conversion into heat at a certain
temperature and pressure.
 
ΔH = ΔU + PV
ΔH = change in enthalpy
U = internal energy of the system
PV = pressure in atm times volume in liters

Since the enthalpy is equal to the heat transfer, we can determine the nature
of a reaction from the sign of ΔH:

Exothermic Reaction →ΔH < 0 (negative) → reaction gives

off heat
Endothermic Reaction →ΔH > 0 (positive) → reaction
absorbs heat
 Learning Check
2. Is the following reaction endothermic
or exothermic?
A. CO2(g) + 2H2O(l)  CH4(g) + 2O2(g) ΔH = 890.4 kJ

B. 2SO2(g) + O2(g)  2SO3(g) ΔH = -198.2 kJ

C. CO(g) + 2H2(g)  CH3OH(g) + 90 kJ

D. C6H12O6+ 6О2→ 6CO2 +6H2O + 2808 kJ

23
 Hess’ Law and standard enthalpy of formation
Hess’s Law states that the enthalpy change for any
chemical or physical process does not depend on the
pathway or number of steps required to complete the
process provided that the final and initial reaction
conditions are the same.
According to Hess’s law the heat of the
reaction depends on Initial and final conditions
of reactants;
We can use these values to calculate the enthalpies
of many reactions, using the following formula:
ΔHrxn= Σn×Hf°(products) − Σm×Hf°(reactants)
n and m are the number of moles of each product and
reactant.
 Hess’ Law and standard enthalpy of formation
The standard state of an element or compound is
its stable form at 25°C (~ room temperature) under
1 atmosphere pressure (ambient pressure).

Standard Enthalpy of Formation (ΔHf° ) - the

change in enthalpy when one mole of a substance in
the standard state is formed from its pure elements
under the same conditions.

ΔHf° = 0 for elements already in their standard

state (i.e. N2(g), Au(s), Cl2(g), etc.)

ΔHf° values have been experimentally determined

Research of thermochemical calculations for the
energy performance of biochemical processes
The energy is given mainly fats, proteins, carbohydrates:
39.9 kJ/g, 17 kJ/g, 17 kJ/g, respectively.
Although they have different biochemical mechanism and
thermochemical reactions produced the same quantity of
products: CO2 and H2O.

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 Energy value of the food

Food Energy value, kJ/g

Dairy butter 30.41
Cheddar cheese 16.82
Sugar 16.8
Rice 16.8
Beef meet 11.07
White bread 9.91
Chicken meat 9.54
Eggs 6.12
White fish 3.22
Apples 1.96
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 Learning Check
3. According to Hess’s law the heat of the reaction
depends on______.
A. Initial condition of reactants;
B. Initial and final condition of reactants;
C. Final condition of reactants;
D. Intermediate path of the reaction.
 Entropy
Another important thermodynamic concept is that of entropy.

Unit: Entropy (S) is a measure of the level of disorder or

J/mol•K randomness in a system.
Entropies generally increase with molecular weight;
this is a direct reflection of the principle that
translational quantum states are more closely packed
in heavier molecules.
The entropy of a solid is less than the entropy of a
liquid which is much less than the entropy of a gas.

Change in entropy
according to state
of substance: S > S > S
 The 2nd Law of Thermodynamics
 
The total entropy of a system and its surroundings always
increases for a spontaneous process.

where ΔS – the change in entropy of the system,

Q – amount of heat,
T – temperature.

The change in entropy is equal to the heat

transfer divided by the temperature of the system.
 Standard Entropy
Scientists conventionally set the energies of
formation of elements (ΔHf° for elements)
in their standard states to zero. Entropy,
however, measures not energy itself, but its
dispersal among the various quantum states
available to accept it, and these exist even in
pure elements.

The standard entropy of substance is the entropy of 1

mol/L of it at 1 atm (101.3 kPa) and 298K (25°C).
The Second Law of Thermodynamics and Entropy

Isolated systems spontaneously evolve towards

thermal equilibrium — the state of maximum
entropy of the system.
The entropy of the universe (the ultimate isolated
system) only increases and never decreases.

The significance of entropy is in simply words: all

spontaneous changes in an isolated chemical
system occur with an increase in entropy.
The Second Law of Thermodynamics and Entropy

You can calculate entropy changes during reactions

(ΔS or delta S).
 
ΔSrxn= Σn×S°(products) − Σm×S°(reactants)

where ΔS − entropy change;

ΣS° − sum of standard entropies;
n and m are the number of moles of each product
and reactant.
The 3rd law of thermodynamics

Entropy of perfect crystal at

absolute zero is zero

S0 = 0.

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 Learning Check
4. Which one of the given equations is the
expression of the second law of
thermodynamics?
Gibbs free energy
Free energy is energy that is available to do
work.
Spontaneous reactions release free energy as
they proceed.
Recall that the determining factors for
spontaneity of a reaction are the enthalpy and
entropy changes that occur for the system.
The free energy change of a reaction gives a
criteria for spontaneity at constant pressure
and temperature.
 Gibbs free energy changes

Unit: Free energy or Gibbs free energy (ΔG) is a

kJ/mol mathematical combination of the enthalpy change
and the entropy change at a certain temperature.
ΔG = ΔH − T×ΔS

ΔG – the Gibbs energy change of a reaction;

ΔH – the enthalpy change of a reaction;
T – the absolute temperature (in Kelvin);
ΔS – entropy change of the system.

The change in G can be calculated the same way as

you calculate the change in enthalpy or entropy:
ΔGrxn= Σn×G°(products) − Σm×G°(reactants)
Gibbs free energy changes

1. A reaction is spontaneous only if ΔG is negative

(ΔG<0). Such reactions are said to be
exergonic.

2. A system is at equilibrium and no net change

can take place if ΔG is zero.

3. A reaction is non-spontaneous only if ΔG is

positive (ΔG>0). An input of free energy is
required to drive such a reaction. These
reactions are termed endergonic.
 ΔH, ΔS and Spontaneity of reaction

ΔG = ΔH − T×ΔS

spontaneous at high T
ΔH>0 ΔS>0 ΔG</>0
(when T×ΔS is large)

ΔH>0 ΔS<0 ΔG>0 non-spontaneous

ΔH<0 ΔS>0 ΔG<0 spontaneous

spontaneous at low T
ΔH<0 ΔS<0 ΔG</>0
(when T×ΔS is small)
 Learning Check
5. Spontaneous reactions are driven by:
1. Low enthalpy values and high entropy values;
2. Low enthalpy values and low entropy values;
3. High enthalpy values and low entropy values;
4. High enthalpy values and high entropy values.
Laws of Thermodynamics as Related to Biology

 The laws of thermodynamics are important unifying principles of biology.

These principles govern the chemical processes (metabolism) in all
biological organisms. The First Law of Thermodynamics, also known ​as
the law of conservation of energy, states that energy can neither be created
nor destroyed. It may change from one form to another, but the energy in a
closed system remains constant.
 The Second Law of Thermodynamics states that when energy is
transferred, there will be less energy available at the end of the transfer
process than at the beginning. Due to entropy, which is the measure of
disorder in a closed system, all of the available energy will not be useful to
the organism. Entropy increases as energy is transferred.
 In addition to the laws of thermodynamics, the cell theory, gene theory,
evolution, and homeostasis form the basic principles that are the foundation
for the study of life.
 First Law of Thermodynamics in Biological
Systems
 All biological organisms require energy to survive. In a closed
system, such as the universe, this energy is not consumed but
transformed from one form to another. Cells, for example, perform a
number of important processes. These processes require energy.
In photosynthesis, the energy is supplied by the sun. Light energy is
absorbed by cells in plant leaves and converted to chemical energy.
The chemical energy is stored in the form of glucose, which is used
to form complex carbohydrates necessary to build plant mass.
 The energy stored in glucose can also be released through cellular
respiration. This process allows plant and animal organisms to
access the energy stored in carbohydrates, lipids, and other
macromolecules through the production of ATP. This energy is
needed to perform cell functions such as DNA replication, mitosis,
meiosis, cell movement, endocytosis, exocytosis, and apoptosis.
Second Law of Thermodynamics in Biological Systems

 As with other biological processes, the transfer of energy is not 100 percent
efficient. In photosynthesis, for example, not all of the light energy is
absorbed by the plant. Some energy is reflected and some is lost as heat.
The loss of energy to the surrounding environment results in an increase of
disorder or entropy. Unlike plants and other photosynthetic organisms,
animals cannot generate energy directly from the sunlight. They must
consume plants or other animal organisms for energy.
 The higher up an organism is on the food chain, the less available energy it
receives from its food sources. Much of this energy is lost during metabolic
processes performed by the producers and primary consumers that are
eaten. Therefore, much less energy is available for organisms at higher
trophic levels. (Trophic levels are groups that help ecologists understand the
specific role of all living things in the ecosystem.) The lower the available
energy, the less number of organisms can be supported. This is why there
are more producers than consumers in an ecosystem.
 Living systems require constant energy input to maintain their highly ordered
state. Cells, for example, are highly ordered and have low entropy. In the
process of maintaining this order, some energy is lost to the surroundings or
transformed. So while cells are ordered, the processes performed to maintain
that order result in an increase in entropy in the cell's/organism's
surroundings. The transfer of energy causes entropy in the universe to
increase.
Living organisms as open systems
They permanently take up nutrients with the high enthalpy
and low entropy
Nutrients are converted to waste products with low
enthalpy and high entropy
Energy extracted from nutrients is used to power
biosynthetic processes and keep highly organized
cellular structure
A part of energy is converted to heat
Living organism can never be at equilibrium
Steady state - open systems in which there is a constant
influx of reactants and removal of products
Reactions are arranged in series, product of one reaction
is a substrate of the following reaction
Reactions in living organisms are arranged in series,
product of one reaction is a substrate of the following
reaction
Processes
exergonic endergonic

Endergonic reactions can proceed only in

coupling with exergonic reactions

Transfer of energy from one process to another

process in enabled by „high-energy“ compounds
Mostly ATP is used.
Phosphoryl group PO32- is transferred from one
to another compound in process of coupling
 Principles of coupling
Coupled reactions
A+ B ⇌C +D ∆G1 > 0
D+E⇌F+G ∆G2 < 0

A + B + E ⇌ C + F + G ∆G3 = ∆G1 + ∆G2 < 0

The exergonic hydrolysis of macroergic compound is

coupled with the endergonic process by transferring a
phosphate group to another molecule.
Principles of coupling
The exergonic hydrolysis of ATP is coupled with the
endergonic glucose-6-phosphate formation process by
transferring a phosphate group to another molecule.
 The other high-energy compounds

Compounds that by hydrolytic cleavage provide

energy that is comparable or higher than ΔG°´ of
ATP hydrolysis

Most often derivatives of phosphoric acid containing

phosphate bonded by:
anhydride
amide
enolester bond

(esters of phosphoric acid are not macroergic

compounds)
 Learning Check
6. What kind of thermodynamic system is
the living organism?

А. Opened system;
B. Closed system;
C. Isolated system.
 ΔH, ΔS & ΔG
Determination of type of a reaction if you know:
an enthalpy change ΔH or heat Q :
 an exothermic reaction: ΔH<0 or Q>0
an endothermic reaction: ΔH>0 or Q<0

an entropy change ΔS shows degree of randomness

in the system:
 ordering at ΔS<0
disordering at ΔS>0

an Gibbs free energy changes ΔG :

a spontaneous reaction at ΔG<0
a non-spontaneous reaction at ΔG>0
 Calculate the Gibbs free-energy change (ΔG) at t=45°C for the
reaction H2(g)+N2(g)⇌N2H4(l). 
Ex. 1
If ΔH°(N2H4) = 50.6 kJ/mol,  
S°(N2H4)=121.2 J/mol·K, S°(N2)=191.6 J/mol·K,
S°(H2)=130.7 J/mol·K. Is the reaction spontaneous?
Solution:
1st: Balance this reaction. 2H2(g)+N2(g)⇌N2H4(l).
2nd: Find ΔHrxn= ∑nΔH°(products) − ∑mΔH°(reactants)
because ΔH°(H2)=ΔH°(N2)=0 kJ/mol
ΔHrxn=1mol•ΔH°(N2H4) − (2mol•ΔH°(H2)+1mol•ΔH°(N2)) =
1•50.6 − (2•0+1•0) = 50.6 kJ
3rd: Find ΔSrxn= ∑nΔS°(products)−∑mΔS°(reactants)
ΔSrxn= 1mol•ΔS°(N2H4) − (2mol•ΔS°(H2)+1mol•ΔS°(N2)) =
1•121.2 − (2•130.7+1•191.6) = -331.9 J = -0.3319 kJ
4th: Find T = t°C+273K = 45+273= 318K
5th: Find ΔG = ΔH−TΔS
ΔG = 50.6 − 318•(-0.3319) = 156.1442 kJ
Ex. 2
Calculate caloric value of a food, which contains 63.7 g fats, 45.4 g
carbohydrates and 18.2 g proteins,
if the ∆Н°c(fats) = -39.9 kJ/g, ∆Н°c (carb.) = -17 kJ/g,
∆Н°c (prot.) = -17 kJ/g.

Solution:
1st: Find ∆Н for 180 g of eggs:
∆Н (fats) = -39.9 kJ/g × 63.7 g = -2541.63 kJ
∆Н(carb.) = -17 kJ/g × 45.4 g = -771.8 kJ
∆Н (prot.) = -17 kJ/g ×18.2 g = -309.4 kJ

2nd: ∆Н (food) = ∆Н (fats) + ∆Н(carb.) + ∆Н (prot.)

∆Н (food) = -2541.63 + (-771.8) + (-309.4) = -3622.83 kJ

3rd: Convert from kJ to caloric value:

∆Н (food) = -3622.83 kJ × 0.239 = -865.86 Cal

Ans: ∆Н (food) = -865.86 Cal.

Thank you for your
attention!