BIO 202 Biochemistry II

by
Seyhun YURDUGÜL

Lecture I
Basics of Thermodynamics
 Content Outline
• Definition
• The laws of thermodynamics
• The free energy concept
 What is thermodynamics?
• the field of physics that studies the
properties of systems
• that have a temperature
• and involve the flow of energy from one
place to another.
 Laws of thermodynamics

• Zeroth Law
• First Law
• Second Law
Another demonstration for Zeroth
Law
 Heat

• defined as energy in transit from a high

temperature object
• to a lower temperature object.
• An object does not possess "heat";
• the appropriate term for the microscopic
energy in an object: internal energy.
 Heat
• The internal energy :
• may be increased by transferring energy to
the object from a higher temperature
(hotter) object –
• this is properly called heating.
Heat
 Specific Heat

• amount of heat per unit mass required to raise the

temperature by one degree Celsius.
• The relationship between heat and temperature
change:
• usually expressed in the form shown below where
c is the specific heat.
• does not apply if a phase change is encountered,
• because the heat added or removed during a phase
change does not change the temperature.
 Specific Heat
• The specific heat of water:
• 1 calorie/gram °C = 4.186 joule/gram °C
• higher than any other common substance.
• As a result, water plays a very important
role in temperature regulation.
• The specific heat per gram for water :
• much higher than that for a metal.
Specific Heat
 Heat Transfer

• normally from a high temperature object to

a lower temperature object.
• changes the internal energy of both systems
involved according to the First Law of
Thermodynamics.
 Heat Conduction

• heat transfer by means of molecular agitation

within a material without any motion of the
material as a whole.
• If one end of a metal rod : at a higher temperature,
then energy : transferred down the rod toward the
colder end,
• because the higher speed particles:
• collide with the slower ones with a net transfer of
energy to the slower ones
 Heat Convection

• heat transfer by mass motion of a fluid such as air or

water;
• when the heated fluid is caused to move away from the
source of heat, carrying energy with it.
• Convection above a hot surface occurs
• because hot air expands, becomes less dense, and rises (as
like in Ideal Gas Law).
• Hot water : likewise less dense than cold water and rises,
causing convection currents which transport energy.
Heat Convection
Heat Transfer by Vaporization

• If part of a liquid evaporates,

• it cools the liquid remaining behind
• because it must extract the necessary heat of
vaporization from that liquid;
• in order to make the phase change to the
gaseous state.
Heat Transfer by Vaporization
• therefore an important means of heat
transfer in certain circumstances:
• such as the cooling of the human body
• when subjected to ambient temperatures
above the normal body temperature
Explanation of the figure for Zeroth
Law
• If A and C: in thermal equilibrium with B,
• then A : in thermal equilibrium with B.
• Practically this means that all three are at
the same temperature,
• and it forms the basis for comparison of
temperatures.
• so named because it logically precedes the
First and Second Laws of Thermodynamics
 More on first law of
thermodynamics
• In the context of physics, the common
scenario:
• one of adding heat to a volume of gas
• and using the expansion of that gas to do
work,
• as in the pushing down of a piston in an
internal combustion engine.
 More on first law of
thermodynamics
• The first law of thermodynamics:
• the application of the conservation of
energy principle to heat and thermodynamic
processes:
 More on first law of
thermodynamics
• It is just that
• W : defined as the work done on the system
instead of work done by the system.
Isothermal Process
 Adiabatic Process

• An adiabatic process :
• one in which no heat gained or lost by the system.
• The first law of thermodynamics with Q=0 shows
that:
• all the change in internal energy is in the form of
work done.
• This puts a constraint on the heat engine process
leading to the adiabatic condition
• can be used to derive the expression for the work
done during an adiabatic process.
 Isothermal Process

• For a constant temperature process

involving an ideal gas,
• pressure can be expressed in terms of the
volume:
 Pressure-Volume (PV) Diagrams

• Pressure-Volume (PV) diagrams:

• a primary visualization tool for the study of heat
engines.
• Since the engines usually involve a gas as a
working substance,
• the ideal gas law relates the PV diagram to the
temperature
• so that the three essential state variables for the
gas:
• can be tracked through the engine cycle.
 Pressure-Volume (PV) Diagrams

• Since work is done only

• when the volume of the gas changes,
• the diagram gives a visual interpretation of
work done.
 Pressure-Volume (PV) Diagrams
• Since the internal energy of an ideal gas depends
upon its temperature,
• the PV diagram along with the temperatures
calculated from the ideal gas law
• determine the changes in the internal energy of the
gas
• so that the amount of heat added can be evaluated
from the first law of thermodynamics.
 Pressure-Volume (PV) Diagrams

• In summary, the PV diagram:

• provides the framework for the analysis of
any heat engine
• which uses a gas as a working substance.
 Pressure-Volume (PV) Diagrams

• For a cyclic heat engine process, the PV

diagram will be closed loop.
• The area inside the loop:
• a representation of the amount of work done
during a cycle.
 Pressure-Volume (PV) Diagrams

• Some idea of the relative efficiency of an

engine cycle:
• can be obtained by comparing its PV
diagram with that of a Carnot cycle,
• the most efficient kind of heat engine cycle
Pressure-Volume (PV) Diagrams
Adiabatic Process
Constant Volume Process
 System Work

• When work:
• done by a thermodynamic system,
• it is usually a gas that is doing the work.
• The work done by a gas at constant pressure
is:
Work at constant pressure:
 Enthalpy
• It is a useful quantity for tracking chemical
reactions.
• If as a result of an exothermic reaction some
energy is released to a system,
• it has to show up in some measurable form
in terms of the state variables.
 Enthalpy
• An increase in the enthalpy H = U + PV:
• might be associated with an increase in
internal energy,
• which could be measured by calorimetry,
• or with work done by the system, or a
combination of the two.
 Internal Energy
• The internal energy U :
• thought of as the energy required to create a
system in the absence of changes in temperature or
volume.
• But if the system: created in an environment of
temperature T,
• then some of the energy can be obtained by
spontaneous heat transfer;
• from the environment to the system.
 Helmholtz free energy
• But as discussed in defining enthalpy,
• an additional amount of work PV must be done
• if the system is created from a very small volume
in order to "create room" for the system.
• an environment at constant temperature T will
contribute an amount TS to the system:
• reducing the overall investment necessary for
creating the system.
 Helmholtz free energy
• This net energy contribution for a system
created in environment temperature T from
a negligible initial volume :
• Gibbs free energy.
 Free energy (ΔG)
• Defined as ‘Gibbs free energy’
• The energy which has an ability to carry out
work
• Standard version (ΔG) : performed in
conditions as 1 M concentrates, 25 C
temperature and 1 atm(760 mm Hg)
pressure
Another definition by formula for
Gibbs free energy
 Gibbs free energy
• The change in Gibbs free energy, ΔG,
• in a reaction is a very useful parameter.
• It can be thought of as the maximum amount of
work obtainable from a reaction.
• For example, in the oxidation of glucose, the
change in Gibbs free energy:
• ΔG = 686 kcal = 2870 kJ.
• This reaction : the main energy reaction in living
cells.
 Entropy
• The amount of this spontaneous energy
transfer: TS where S is the final entropy of
the system.
• In that case, you don't have to put in as
much energy.
• Note that if a more disordered (higher
entropy) final state is created,
• less work is required to create the system.
 Entropy
• The Helmholtz free energy then:
• a measure of the amount of energy you
have to put in to create a system;
• once the spontaneous energy transfer to the
system from the environment is accounted
for.
Typical example from living
systems
 Why is the heat of vaporization
more at body temperature?
• An interesting feature of the process of cooling the
human body by evaporation that:
• the heat extracted by the evaporation of a gram of
perspiration from the human skin at body
temperature (37°C)
• quoted in physiology books as 580 calories/gm
rather than the nominal 540 calories/gm at the
normal boiling point.
• The question is, why is it larger at body
temperature?
 Why is the heat of vaporization
more at body temperature?
• The main part of the answer
• the binding energy of the water molecules:
• greater at that lower temperature,
• and it therefore takes more energy to break
them apart into the gaseous state.
 Why is the heat of vaporization
more at body temperature?
• The change in the heat of vaporization:
• roughly calculated using what we know
from the specific heat of water,
• 1 calorie/gm °C.
• It takes 37 calories to heat a gram of water
from 0°C to 37°C,
• but the change in the kinetic energy is much
less than that:
Why is the heat of vaporization
more at body temperature?
 Why is the heat of vaporization
more at body temperature?
• the kinetic energy of the water molecules only increases
by:
• 61.7 - 45 = 16.7 calories/gm
• when the water is heated from zero to 100°C
• but we know it takes 100 calories to do that heating.
• Therefore the contribution to weakening the water bonds is
83.3 calories/gm.
• Using the result for water at 37°C :
• 52.4 calories of additional energy must be supplied at 37°C
to vaporize the water
 Why is the heat of vaporization
more at body temperature?
• one additional element in modeling the heat of
vaporization at body temperature:
• - the PdV work required to expand the water into
its gaseous form: slightly less at 37°C.
• By analogy with the work calculation above,
• that work is found to be 34.2 calories/gm,
• 6.8 calories/gm less than at 100°C.
 Why is the heat of vaporization
more at body temperature?
• This model then suggests a heat of
vaporization at 37°C:
• Body temperature heat of vaporization =
539 cal/gm + 52.4 cal/gm - 6.8 cal/gm =
585 cal/gm.
• So this simple model agrees fairly well with
the quoted 580 cal/gm.
 Perspiration Cooling of Body

• When the ambient temperature is above

body temperature, then radiation,
conduction and convection:
• all transfer heat into the body rather than
out.
 Perspiration Cooling of Body

• Since there must be a net heat transfer,

• the only mechanisms left under those
conditions:
• the evaporation of perspiration from the
skin
• and the evaporative cooling from exhaled
moisture.
 Perspiration Cooling of Body

• Even when one :

• unaware of perspiration,
• an amount of about 600 grams per day of
"insensate loss" of moisture from the skin is
observed.
 Perspiration Cooling of Body

• The cooling effect of perspiration

evaporation:
• makes use of the very large heat of
vaporization of water.
• This heat of vaporization:
• 540 calories/gm at the boiling point,
• but is even larger, 580 cal/gm, at the normal
skin temperature.
Why is the heat of vaporization
more at body temperature?
 LITERATURE CITED
• Devlin,T.M. Textbook of Biochemistry with Clinical
Correlations,Fifth Edition,Wiley-Liss Publications,New
York, USA, 2002.
• Lehninger, A. Principles of Biochemistry, Second
edition, Worth Publishers Co., New York, USA, 1993.
• Matthews, C.K. and van Holde, K.E., Biochemistry,
Second edition, Benjamin / Cummings Publishing
Company Inc., San Francisco, 1996.
• Segel, I.H. Biochemical Calculations, Second Edition,
John Wiley and Sons, New York, 1976.