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Bioenergetics and Thermodynamics

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Learning Objectives

At the end of the lesson, students should be able to:

  • Define and describe the free energy
  • Distinguish between endothermic and exothermic reactions
  • Define, describe and distinguish enthalpy and entropy

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Forms of Energy

  • Energy
    • Is the capacity to cause change
    • Exists in various forms, of which some can perform work
  • Kinetic energy
    • Is the energy associated with motion
  • Potential energy
    • Is stored in the location of matter
    • Includes chemical energy stored in molecular structure

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The Laws of Energy Transformation

Thermodynamics

-The branch of science studying heat, energy and the ability of the energy to do work

The First Law of Thermodynamics

(The Law of Energy Conservation)

    • Energy can be transferred and transformed
    • Energy cannot be created or destroyed

“The Amount Of Energy In The Universe Is Constant”

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[Is the study of energy transformations]

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Energy can be converted from one form to another

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An example of energy conversion

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System

Bioenergetics and Thermodynamics

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  • Is the heat content of the reacting system. It reflects the number and kinds of chemical bonds in the reactants and products

Enthalphy (H)

Bioenergetics and Thermodynamics

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Bioenergetics and Thermodynamics

Enthalphy change (∆H)

  • When a chemical releases heat, it is said to be exothermic
  • The heat content of the product is less than that of the reactants; ∆H value has a negative value
  • Reacting systems that take up heat from their surroundings are endothermic; ∆H value has a positive value
  • The units of ∆H is joules/mole or calories/mole

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Enthalphy change (∆H)

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  • According to the second law of thermodynamics
    • Spontaneous changes that do not require outside energy increase the entropy, or disorder, of the universe

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The Second Law of Thermodynamics

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Bioenergetics and Thermodynamics

  • Entropy is the quantitative measure of disorder/randomness in a system

Entropy (S)

Entropy (∆S)

  • When the products of a reaction are less complex and more disordered than the reactants, the reaction is said to proceed with a gain in entropy
  • The units ∆S is joules/mole degree Kelvin

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Particles in:

    • gas are well separated with no regular arrangement.
    • liquid are close together with no regular arrangement.
    • solid are tightly packed, usually in a regular pattern.

Particles in:

    • gas vibrate and move freely at high speeds.
    • liquid vibrate, move about, and slide past each other.
    • solid vibrate (jiggle) but generally do not move from place to place.

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Entropy (S)

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Predicting the sign of ∆S

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Relationship between energy and entropy

  • The change in free energy, ∆G during a biological process is related directly to the enthalpy change (∆H) and the change in entropy

DH = change in enthalpy

DS = change in entropy ; T = degree Kelvin

    • -DG = a spontaneous reaction in the direction written
    • +DG = the reaction is not spontaneous
    • DG = 0 the reaction is at equilibrium

G = ∆HTS

(at constant temperature and pressure)

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Relationship between energy and entropy

G = ∆HTS

(at constant temperature and pressure)

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  • Reaction free-energy depends upon conditions
  • Standard state (DGo) - defined reference conditions

Standard Temperature = 298K (25oC)

Standard Pressure = 1 atmosphere

Standard Solute Concentration = 1.0M

  • Standard transformed constant = DGo’

Standard H+ concentration = 10-7 (pH = 7.0)

H2O concentration = 55.5 M

Standard Free-Energy Change (DGo)

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Go' = standard free energy change (at pH 7, 1M reactants & products); R = gas constant; T = temp)

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  • A living system’s free energy = energy that can do work under cellular conditions
  • Free-energy change (ΔG) is a measure of the chemical energy available from a reaction
    • ΔG = Gproducts - Greactants
  • The free energy change (ΔG) of a reaction determines its spontaneity

Free-Energy Change

Free-Energy Change, ΔG

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  • In a spontaneous reaction:
    • Free energy decreases,
    • ∆G is negative
    • Energy is released by the reaction
    • Reaction is said to be exergonic
  • In a nonspontaneous reaction
    • Free energy increases
    • ∆G is positive
    • Energy is absorbed by the reaction
    • Reaction is said to be endergonic

Free-Energy Change

Free-Energy Change, ∆G

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Energy coupling

    • A spontaneous reaction may drive a non-spontaneous reaction.
    • Free energy changes of coupled reactions are additive.
    • Some enzyme-catalyzed reactions are interpretable as two coupled half-reactions, one spontaneous and the other non-spontaneous.

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For example, in the reaction catalyzed by the Glycolysis enzyme Hexokinase, the half-reactions are:

ATP + H2O ADP + Pi ∆Go' = -31 kJ/mol

Pi + glucose glucose-6-P + H2O ∆Go' = +14 kJ/mol

Coupled reaction:

ATP + glucose ADP + glucose-6-P ∆Go' = -17 kJ/mol

Energy coupling

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Adenosine Triphosphate (ATP)

  • Can carry phosphoryl groups from higher-energy compounds to lower-energy compounds
  • Drives several processes:
    • Biosynthesis of biomolecules
    • Active transport membranes
    • Mechanical work (e.g muscle contraction)

Bioenergetics and ATP

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Phosphoanhydride have a large negative DG of hydrolysis.

“High energy” bonds

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  • ATP (adenosine triphosphate)
    • Is the cell’s energy shuttle
    • Provides energy for cellular functions

O

O

O

O

CH2

H

OH

OH

H

N

H

H

O

N

C

HC

N

C

C

N

NH2

Adenine

Ribose

Phosphate groups

O

O

O

O

O

O

-

-

-

-

CH

The Structure and Hydrolysis of ATP

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Energy

Adenosine triphosphate (ATP)

Inorganic phosphate

Adenosine diphosphate (ADP)

Energy is released from ATP when the terminal phosphate bond is broken (hydrolysed)

The Structure and Hydrolysis of ATP

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  • ATP hydrolysis
    • Can be coupled to other reactions

Endergonic reaction: ∆G is positive, reaction

is not spontaneous

G = +3.4 kcal/mol

Glu

Glu

G = - 7.3 kcal/mol

ATP

H2O

+

+

NH3

ADP

+

NH2

Glutamic

acid

Ammonia

Glutamine

Exergonic reaction: ∆ G is negative, reaction

is spontaneous

P

Coupled reactions: Overall ∆G is negative;

together, reactions are spontaneous

G = –3.9 kcal/mol

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Other examples of high energy compounds

Phosphocreatine

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Other examples of high energy compounds

Phosphoenolpyruvate (PEP)

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An exergonic reaction

    • Proceeds with a net release of free energy and is spontaneous

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Reactants

Products

Energy

Progress of the reaction

Amount of

Energy released �(∆G <0)

Free energy

(a) Exergonic reaction: energy released

Exergonic and Endergonic Reactions in Metabolism

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  • An endergonic reaction
    • Is one that absorbs free energy from its surroundings and is nonspontaneous

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Energy

Products

Amount of

Energy released �(∆G>0)

Reactants

Progress of the reaction

Free energy

(b) Endergonic reaction: energy required

Exergonic and Endergonic Reactions in Metabolism

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  • Reactions in a closed system
    • Eventually reach equilibrium

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  1. A closed hydroelectric system.

Water flowing downhill turns a turbine that drives a generator providing electricity to a light bulb, but only until the system reaches equilibrium.

G < 0

∆G = 0

Equilibrium and Metabolism

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    • Experience a constant flow of materials in and out, preventing metabolic pathways from reaching equilibrium

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(b) An open hydroelectric � system. Flowing water� keeps driving the generator � because intake and outflow � of water keep the system � from reaching equlibrium.

G < 0

Cells in our body

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  • An analogy for cellular respiration

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(c) A multistep open hydroelectric system. Cellular respiration is � analogous to this system: Glucoce is broken down in a series� of exergonic reactions that power the work of the cell. The product� of each reaction becomes the reactant for the next, so no reaction � reaches equilibrium.

G < 0

G < 0

G < 0

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Think!

What does ΔG tell us about a biochemical reaction?

  • A reaction occurs spontaneously only if ΔG <0 (exothermic or exergonic)
  • A system is at equilibrium when ΔG = 0 (steady state)
  • A reaction in which ΔG>0 requires input of energy (endothermic or endergonic)
  • ΔG = Gproducts – Greacants, it does not depend on the reaction path (i.e. combustion vs metabolism)
  • ΔG provides no information on the reaction rate

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