Flow of Energy in Nature.

The First Law of

Thermodynamics
Beki Kan
Learning Objectives
• State the basic stages of energy transfer in nature
• Understand how biological systems obey the laws of
thermodynamics
• Define macroscopic properties; system, surroundings
and boundary; intensive and extensive properties;
energy, heat and work; internal energy; enthalpy and
heat capacity
• Learn different types of system and their properties
• State the first law of thermodynamics and infer its
implications
References

• Bioenergetics by A.Lehninger
• Biological Thermodynamics by D.T.Haynie
• Physical Chemistry with Biological Applications
Laidler
• Physical Chemistry for the Life Sciences P.Atkins
& J de Paula
• Molecules of Life John Kuriyan et al.
Bioenergetics and the Flow of Energy in
Nature
• Bioenergetics: The study of energy transformations in
living organisms.
• All organisms are alike in that they must capture,
transduce, store and use energy in order to live.
• The concept of energy is the most basic one of all of
science and engineering.
• Biological Energy Transformations: three major stages
through the biological world
• Photosynthesis
• Respiration
• Work
 Photosynthesis
• The sun generates radiant
energy from nuclear fusion
reactions.

• Only a tiny fraction (much less

than 1%) of this energy
reaches us.

• Capture of radiant energy by

chlorophyll in green plants and
transformation into chemical
energy is stored in the form of Molecular Biology of the Cell. 3rd edition.
Alberts B, Bray D, Lewis J, et al. New
chemical bonds York: Garland Science; 1994.

Solar energy
6CO2 + 6H2O Chlorophyll
C6H12O6 + 6O2 ΔG= +686 kcal/mole
 E = hc/λ = hν

—λ, wavelength of light;

—ν, photon frequency;
—E, photon energy;
—c, speed of light in vacuo;
—h, Planck’s constant

www.life.illinois.edu/govindjee/paper/fig1.gif
Respiration

The chemical energy of carbohydrates and other

foodstuff molecules is transformed into a more
directly useful kind of energy during their oxidation
in cells of animals.

C6H12O6 + 6O2 6CO2 + 6H2O, ΔG= -686 kcal/mole*

* used for ATP synthesis

Work
• The chemical energy recovered from foodstuff molecules by
oxidation is used by cells to do work, either within themselves or on
the environment.
— Mechanical work
— Osmotic work
— Electric work
— Chemical work of growth
— Generation of heat

• These biological processes involve a huge number of specific

biochemical reactions, each of which requires energy in order to
proceed.

• As these functions are performed, energy finally flows to the

environment in a dissipated, useless form.
Two of the Requirements for Life

• Mechanisms to control energy flow

• For ex: membrane-bound protein machines involved in
photosynthesis
• Mechanisms for the storage and transformation of
biological information
• Structures of the protein enzymes that regulate the flow of
energy and information in a cell are encoded by nucleic acids
within the cell.
Some Important Points

— Order is a basic characteristic of living

organisms.
— ATP plays the role of the main energy ‘currency’
of biochemical processes in all known organisms.
— In the course of energy transformations, the
total amount of energy is always constant.
Thermodynamics and Bioenergetics
• Branch of physics that deals with energy and its
transformations (storage, transformation and
dissipation).
• Therme: heat; dynamics: power in Greek

• Biological systems comply with the laws of

thermodynamics.
• Bioenergetics is the quantitative study of
— energy transductions-changes of one form of energy into
another- that occur in living cells,
— the nature and function of the chemical processes
underlying these transductions.
Conservation of Energy Applying to
Biological Systems
• Lavoisier and Laplace in 1777.
— An animal was placed in a block of ice in an insulated enclosure
— By observing the rate at which the ice melted, the total energy
given up as heat by the animal was estimated.
— The amount of food the animal used up was roughly correlated
with the energy released.
• Rubner, 1885, Benedict, Atwater and Ross
Rubner’s Experiment
• The total heat given off by a
dog was measured
calorimetrically.
• At the same time, O2 intake
and release of CO2 and H2O
were measured.
• These two end products can
be used to measure the
chemical energy consumed.

Ref: www.nu.ac.za/.../image012.jpg
Ref: www.fkm.utm.my/~nazrikh/smj3403/Intro_2b.gif
Macroscopic Properties of Matter

• Thermodynamics studies the general relationships which

exist between macroscopic properties of matter.
— Macroscopic properties: relating to large assemblies of
molecules (very large number of similar particles, >109);
— P, V, T.

— Microscopic properties: relating to individual molecules;

light absorption, diffusion
Laws of Thermodynamics
• They are statements about the interchange of energy
among substances
• Two properties particularly important in explaining the
behavior of matter
• Energy
• Entropy
• The first law of TD: The energy of the universe remains
constant. Energy can neither be created nor destroyed.
• The second law of TD: The entropy of the universe is
constantly increasing.
• TD makes a profound contribution to the understanding
of living systems.
The Thermodynamicist’s Picture of the
World
• TD theory depicts the world in a
highly simplified fashion. Each object
is characterized by a small number of
uniform properties T, P, E.
• Part of the world that is selected for
consideration is called the SYSTEM.
• The region around the system (the
entire universe excluding the system)
is the SURROUNDINGS.
• The surface dividing the system from
the surroundings is called the
BOUNDARY.
 Different Types of System
• Closed system: It can exchange heat (and work) but not matter with
its surroundings. Thus, the boundary is impermeable to matter
• Example: a test tube with a stopper

• Open system: It has a boundary which allows the exchange of

matter, heat and work with its surroundings.
• Example: a fertilized egg being hatched by a hen.
• O2 comes in CO2 goes out of the egg & heat is also exchanged
• Isolated system: The boundary permits neither matter nor energy to
enter or exit.
• Example: the universe

• Adiabatic system: Heat and matter can not pass through the
boundaries but work can be done.
Examples of Thermodynamic Systems

http://www.mikeblaber.org/oldwine/BCH4053/Lecture04/Lecture04.htm

Isolated system: there is no mass and energy transfer across the boundary
Closed system: heat but not matter passes between the system and
surroundings
Open system: both heat and matter pass between the system and
surroundings
Examples of Open Systems

www.geo.arizona.edu/xtal/nats101/4_5.jpg

Automobile engine: Muscles of a runner’s legs:

Doing work on its surroundings. Glucose plus oxygen in, CO2
Heat also crosses the boundary. out. Work on bones.
Heat

Heat, Q, or thermal energy is a form of kinetic

energy, energy arising from motion.

Heat is the change in energy of a system that

results from its temperature differing from that
of its surroundings.
Energy
Energy is a complex concept – for now define it as “the
ability to do work” – not strictly valid, for example, energy
associated with heat is often not available to do work.
Forms of energy
mechanical
heat
light
chemical
electrical
nuclear
Energy has units of Joules or calories (J, kJ and cal, kcal).
4.18 joule = 1 cal
Ref: www.solar-benefits.com/index.5.gif
Carbon, Energy and Life
The energy of a C-C bond is about twice as great as N-N bonds or O-O
bonds.

www.windows.ucar.edu/.../carboncycle_sm.jpg
The First Law of Thermodynamics

■ Thermodynamics is generalized from experience & is not

derived from any other law or principle.
■ It was based mainly on experiments done in 1800’s in which
mechanical energy was converted into heat. Other forms of
energy such as radiation, chemical bonding etc. were later
included.
■ The first law is empirical in nature.
◻ It cannot be derived mathematically from more basic
principles.
■ It has been tested many times and it has not been violated
even once thus far.
■ The first law makes energy the most important concept in
physics.
Internal Energy
■ The energy within a system (U)

■ The energy of a substance in the absence of external effects

■ Those kinds of energy that can be modified by chemical processes

(for our purposes*)
◻ Translational
◻ Vibrational
◻ Rotational
◻ Bonding and non-bonding energies

■ As with heat, both internal energy and work are measured in units
of joules or calories.

■ It is a state function (its value depends on the current state of the

system and not on how that state was prepared)
* nuclear energy does not change in any chemical or biochemical reaction
Internal Energy and the State of a
System
■ The thermodynamic state is defined by giving any two of three variables,
❖ the temperature, T,
❖ the pressure of the system, P, and
❖ the volume of the system, V;
❖ PLUS the amounts of all substances present.

■ The internal energy is a function of the STATE of a system.

■ The thermodynamic state is like a recipe for producing the system in a

defined way:
◻ For ex., a system composed of 1 mol O2 gas in 1 l at 273 K will have a defined
state and therefore a defined internal energy value.

■ This value is independent of the past history of the system.

Variables of State
■ They depend only on the state of a system & not on how the system
arrived at that state i.e. they depend on the conditions at the time of
measurement.
◻ For example for a pure liquid : P, T, V. These are sufficient to specify
many other properties like density, energy etc.
◻ Heat & work are not variables of state because they depend specifically
on the method used to change from one state to another.
■ Two kinds of properties of state are defined:
◻ Intensive and Extensive Properties.
◻ Intensive Properties are those which when measured in any part of the
system have the same value. For ex. temperature, pressure.
◻ Extensive Properties are additive properties. The measured values in
parts of the system have to be added to obtain the value for the
system. For ex. mass, volume, internal energy; the value depends on
the amount of the substance
Work, Energy and Heat
■ The essence of the first law : Both heat and work are
forms of energy.

■ The bulk (macroscopic) properties of matter are

determined by motion and types of potential energy of
individual particles and their interaction energies.

■ More convenient to describe these properties in terms of

T, P, V of the whole system and the ability of the system
to do work.
Work
■ Energy transfer by organized motion

■ Energy exchange between system & surroundings is only in the

form of heat & work in a closed system

■ The simplest kind of work is done when a force acts on an object

over some distance.
W = external force X displacement
The product of the magnitude of the displacement and the component
of the force parallel to the displacement

■ Work can be converted into potential energy (when we lift an

object)

■ Work can also be converted into heat (pushing a brick along a

floor); no further work can be done.
Heat and Work
■ Both heat and work are forms of
energy transfer across the boundary
of a system

■ Difference
◻ Work is the equivalent of a force
acting through the displacement
of an object, while heat is energy
transfer due to a temperature
difference.
◻ Work involves the non-random
movement of particles, heat
involves the random movement of
particles
 Work Sign Work
convention
■ Work in biological systems
◻ Mechanical: chromosomal movement
in metaphase, migration of cells,
muscular contraction + positive Work done on the
◻ Chemical potential: diffusion of system by
chemical species. surroundings*. Energy
◻ Electrical: transfer in neurons, of the system
extract energy from sun, pumping of increases.
ions across a membrane
- negative Work done by the
◻ Pressure-volume work: expansion or
contraction of a gas, in gas system. Energy of
exchanging organs the system
decreases.
In all these examples, a force is exerted
against a resistance to produce
displacement, and work is done. * The system is compressed by an external
pressure
How Do We Calculate Work?
1. Work of compressing or extending a spring (elastic
work)
◻ F = -k.(x – x0 ) muscle fiber work

2. Pressure – volume work

U2
◻ w=- ∫ U1
Pop dV or Pop.ΔV where ΔV can be + or –

3. Work in gravitational field

◻ W = m.g.( h2 – h1 )

4. Electrical work
◻ W = - E.I.t E= voltage, potential; I= current; t = time
 Heat
■ Heat is defined as the quantity
(form of energy) that changes
the temperature. Sign Heat
◻ Temperature = average convention
kinetic energy of translational
motion
+ positive Heat transferred to the
■ Ability to change the system from the
temperature of an object environment

- negative Heat transferred to the

environment
Relation between Work and Heat: The
First Law
■ For any system considered, the increase in internal
energy, ΔU, is equal to the heat absorbed by the system,
Q plus the work done on the system, W.

ΔU = Q + W

■ Energy can neither be created nor destroyed. The

energy of the universe is constant.
 The first law of thermodynamics:
Conservation-of-energy principle stated for a
system in thermal equilibrium.

Ref: http://philschatz.com/physics-book

Note: Q is positive for net heat transfer into the system. More work is
done by the system than on it. therefore –W. Note also that if more heat
transfer into the system occurs than work done, the difference is stored
as internal energy.
The First Law. Example: Boiling
Teakettle

This boiling tea kettle represents energy in motion. The water in the kettle is turning to
water vapor because heat is being transferred from the stove to the kettle. As the
entire system gets hotter, work is done—from the evaporation of the water to the
whistling of the kettle. (credit: Gina Hamilton) http://philschatz.com/physics-book
The change in internal energy of a system equals the net heat transfer into the system
minus the net work done by the system.
The First Law. Example

The energy of a gas increases by 0.4 J when it is compressed by a force of 1

newton acting through 0.5 meter. Calculate the heat change.

W= f X d = (1 nt) (0.5 m)= +0.5 J

ΔU = Q + W
Q= ΔU – W= 0.4- 0.5 = -0.1 J

Q is negative therefore heat is released when the gas is compressed.

The First Law and Metabolism

Heat transferred out of the body and work done by the body remove internal
energy, while food intake replaces it. (Food intake may be considered as
work done on the body.) (b) Plants convert part of the radiant heat transfer
in sunlight to stored chemical energy, a process called photosynthesis.
http://philschatz.com/physics-book
The First Law and Metabolism: Example

■ If a woman does 500 J of work and 9500 J of

heat transfer occurs into the environment in
the process, what is the change in her internal
energy, assuming no change in temperature
or consumption of food? (That is, there is no
other energy transfer.)
■ Answer: -10,000 J (decrease in internal energy)
Two Different Sign Conventions for
the Work Term
■ In the older textbooks, the first law appears as:
◻ ΔU= Q - W.

■ In this case (+) w is defined as the work done by the system on the
surroundings.

■ In more modern texts:

◻ ΔU= Q + W.

■ In this case, (+) w is defined as the work done on the system by

the surroundings.
Examples of the Application of the First
Law

Work
Gas heat

Water bath, constant T

Work is done on a gas enclosed in a cylinder by moving the piston (+dW).

Compressing the gas produces heat, released through the cylinder wall to
the surrounding constant temperature bath (-dQ).

dU= -dQ + dW = dW- dQ

Examples of the Application of the First
Law

CH4 + 2O2 CO2 +2H2O heat

Water bath, constant T

▪ A convenient system for the measurement of heat of a chemical reaction.

▪ Methane and oxygen mixed and ignited. Large constant T water bath absorbs the
reaction heat. Heat is released (-dQ). Constant V vessel; therefore no work.
▪ dU= -dQ
The Isothermal Nature of Cellular
Processes
First law says that heat and work are forms of energy.
* However, they are not completely equivalent

W Q

Example: Turning paddlewheel in water. Temperature of water ↑

Will cooling the water turn the paddlewheel??

The Isothermal Nature of Cellular
Processes
■ Heat engines (steam engines)
◻ W = Q (T1-T2) / T1

■ A temperature differential is needed in order

to do work.

■ The maximum work depends on the initial and

final temperatures of a machine.

◻ Living organisms are essentially

isothermal.
◻ In biological systems, there is a restriction.
Chemical reactions occur under isothermal
conditions.
■ Temp change under 10C. This means
that heat cannot be converted into
work under any circumstances.
Enthalpy or Heat Content
■ If we consider chemical processes involving gases or
uncharged systems, all work if P-V work.

■ If the volume is constant, the work, PΔV is 0 and by the

first law, the increase in internal energy is just the heat
absorbed at constant volume: ΔU= Qv

■ It is fairly common in a chemical reaction for the volume

to change, but P to be constant.
Enthalpy or Heat Content
■ Under these conditions, ΔU is not an appropriate quantity to
characterize chemical changes and another function that is more
useful, enthalpy,H, is used.

■ We define a new state variable, that is a combination of other state

variables:
◻ Enthalpy = H = U + PV
■ U = energy of the system

■ P = pressure of the system

■ V = volume of the system

Enthalpy or Heat Content
When the pressure is constant and the system expands from V1 to V2,
the system does work on the surroundings;
work is = - P Δ V

■According to the first law, Δ U = Qp + W= Qp - P Δ V

■Qp= U2-U1 + P (V2-V1)
■Q p = Δ U + P Δ V

We have defined Enthalpy = H = U + PV

Therefore: ΔHp = Qp

■When the only work is P-V work, the increase in enthalpy is equal to
the heat absorbed at constant pressure and that equals ΔU + P Δ V
Enthalpy or Heat Content

■ Part of the heat absorbed at constant P increases the energy of the

system and part goes to expand the system against external
pressure.
i.e. At constant pressure, the change in internal energy is equal to
heat absorbed by the system or heat given to surroundings.

■ In biology, processes occur at constant pressure rather than

constant volume (ex: metabolic, digestive) and they involve small
changes in volume.
■ If ΔV = 0 as in liquids and solids, work done = 0;
i.e. W = 0
***and so : ΔH = Qp = ΔU
 Enthalpy or Heat Content

■ ΔH is a property of the system like P,T,V. i.e. it does not

depend on path but on the conditions of state.

■It is an extensive property, that is, it is additive.

■Not the absolute value of H but change of enthalpy

between two states is important.

***
Enthalpy or Heat Content
■ Enthalpy is the heat content of reacting systems.

■ It reflects the number and kinds of chemical bonds in

the reactants and products.

■ Enthalpy is released or absorbed in a chemical reaction

when bonds are formed or broken; thus the overall
change in enthalpy; ΔH, is equal to the overall change in
bond energies.
Heat Capacity
■ Relation between the quantity of
heat added and the number of
degrees of temperature change.

■ Heat capacity: experimental

quantity, which characterizes how
much heat is necessary to raise
the temperature by 1 degree
Celsius.
◻ Unit is ; J/K.mol or cal/K.mol

■ C of substance will increase with

increasing temperature. It also
depends on P & V. For gases C is
denoted as Cp at constant Specific heat: amount of heat required
pressure & C is denoted as Cv at to raise the temperature of 1 g of
constant Volume. substance by 1 degree Celsius.
Heat Capacity: Example
■ How much heat is required to raise the temperature
a)of 250 g of H2O by 10oC? (Specific heat= 1 cal/g oC)
b) of brass (Specific heat= 0.09 cal/g oC)

Heat Capacity= Specific heat X M.Wt.

◻ Q= smΔT= (1 cal/goC) (250 g) (10 oC)

■ = 2500 cal water
◻ Q= smΔT= (0.09 cal/goC) (250 g)(10 oC)
■ = 225 cal brass

■ Illustrates that water has a very large heat capacity. This makes it a good
temperature regulator.

■ One of the reasons that the temperature of biological systems does not
show a very large fluctuation

■ Fever of 40oC represents a great deal of internal energy (since the body is
mostly water)
Thermochemistry. The Application of
the Enthalpy Concept
■ Traditionally, an enthalpy change
is called a “heat”
H vap (heat of vaporization); ΔH
sol
(heat of solution)

ΔH ice,H2O (ice melts); ΔH H2O,vap

(water vaporizes)

Enthalpy change of mucle

contraction
If ΔH is negative (−) the reaction
is called exothermic. It
Enthalpy change of separation
of daughter chromosomes liberates energy.

Enthalpy change of folding of If ΔH is positive (+) the reaction

a newly synthesized protein is called endothermic. It
absorbs energy.
 ΔH is Experimentally Measured by
Bomb Calorimeter
■ Combustion reaction takes place in reaction
vessel.

■ ΔH determined by T change of water.

■ Example:
C6H12O6 + 6O2 6CO2 + 6H2O, ΔH = − 673 kJ/mol
www.files.chem.vt.edu/.../gra
phics/bomb_cal.gif

www.science- art.com/.../142_11302005164122.jpg
The Standard State
■ The standard state of a system is defined as its most stable form at 1 atm
pressure or for a solute, a concentration of 1 M.

■ Hess’s Law: The enthalpy change of any reaction is the sum of the H
changes of a series of reactions into which the overall reaction may
theoretically be divided.

■ Convention : The “H” of chemical elements (Fe,O2,H2 etc.) at 25°C and 1

atm P is zero.
Molar Enthalpies are Additive: Hess’s
Law
■ The particular reactions into which the overall reaction is divided do not
have to be the usual pathway.

■ The total enthalpy change of a process is equal to the sum of enthalpy

changes of individual steps of the process.

■ Example: Synthesis of acetic acid form its elements:

◻ A. C + 2H2 CH4 ΔH1
C + O2 CO2 ΔH2

CH4 + CO2 CH3COOH ΔH3 (Δ HA =ΔH1 + ΔH2 + ΔH3)

or/

◻ B. 2H2 + O2 2H2O ΔH4

2C + 2H2O CH3COOH ΔH5 (ΔHB=ΔH4+ ΔH5 )

Enthalpy Calculations
■ A B C
If enthalpy of A C is desired .
ΔHAC = ΔHAB + ΔHBC

e.g.(−) CH4 + 2O2 CO2 + 2H2O, ΔH = − 801 kJ/mol

(+) C + O2 CO2, ΔH = − 393k J/mol
(2x) H2 + ½ O2 H2O, ΔH = − 241 kJ/mol

C(graphite) +2H2 CH4 ΔH = −74 kJ/mol

Enthalpy Calculations
■ It is possible to experimentally collect ΔH data for a number of
reactions, tabulate these reactions and their corresponding
enthalpies, and then use those reactions and Hess' Law to calculate
the ΔH for other reactions and enthalpy of formation.

■ The list of heats (enthalpies) of formation can be used to

calculate heats of reactions.
◻ the heatthe heat released or absorbedthe heat released or
absorbed (enthalpy change) during the formation of a pure
substance from its elementsthe heat released or absorbed
(enthalpy change) during the formation of a pure substance
from its elements, at constant pressure and usually denoted by
ΔHf.

■ [To do this we use the equation

ΔH0 (reaction) = ∑ ΔH0f (products) − ΔH0f (reactants) ]
Enthalpy Calculations
■ ΔHreaction . = ∑ΔH products -∑ ΔH reactants
= (H0f C + H0f D) −(H0f A + H0f B)

e.g. C6H12O6 + 6O2 6CO2 + 6H2O

ΔH0 (reaction) = ∑ ΔH0f (products) − ΔH0f (reactants)

ΔH0f for CO2 = (−393 kJ/mol)
ΔH0f for 6CO2 = 6x (−393 kJ/mol)

likewise ΔH0f for 6H2O = 6x (−286 kJ7mol)

ΔH0f for C6H12O6 = −1273kJ/mol and ΔH0f for O2 = 0 (because it is an
element)

❖ ΔH0 (reaction) = -2801 kJ/mol, this is the standard enthalpy of the reaction
of decomposition of glucose into carbon dioxide and water.

■ Experimentally ΔHf is measured by “bomb calorimeter”