thermochemistry © 2009, prentice-hall, inc. chapter 4 thermochemistry thermodynamics dr.imededdine...

Thermochemistry

© 2009, Prentice-Hall, Inc.

Chapter 4

Thermochemistry

Thermodynamics

Dr.Imededdine Arbi NehdiChemistry Department, Science College, King Saud University

Thermochemistry

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• The study of energy and its transformations is known as thermodynamics

• The relationships between chemical reactions and energy changes is an aspect of thermodynamics called thermochemistry

Thermochemistry

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Energy

• Energy is the ability to do work or transfer heat.– Energy used to cause an object that has

mass to move is called work.– Energy used to cause the temperature of

an object to rise is called heat.

Thermochemistry

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Potential Energy

Potential energy is energy an object possesses by virtue of its position or chemical composition.

Fig. 4.1 A bicycle at the top of a hill (left) has a high potential energy. As the bicycle proceeds down the hill (right), the potential energy is converted into kinetic energy; the potential energy is lower at the bottom than at the top.

Thermochemistry

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Kinetic EnergyKinetic energy is energy an object possesses by virtue of its motion.

12

Ek = mv2

where m is mass, v is the speed, and Ek is the kinetic energy.

Thermochemistry

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Units of Energy

• The SI unit of energy is the joule (J).

• An older, non-SI unit is still in widespread use: the calorie (cal).

1 cal = 4.184 J

1 J = 1 kg m2

s2

Thermochemistry

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Definitions:System and Surroundings

• The system includes the molecules we want to study (here, the hydrogen and oxygen molecules).

• The surroundings are everything else (here, the cylinder and piston).

If the hydrogen and oxygen react to form water, energy is liberated. 2 H2 (g) + O2(g) 2 H2O (l) + energyThe system has not lost or gained mass; it undergoes no exchange of matter with its surrounding. However, it does exchange energy with its surroundings in the form of work and heat.

Thermochemistry

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Definitions: Work

• Energy used to move an object over some distance is work.

• w = F dwhere w is work, F is the force, and d is the distance over which the force is exerted.

Thermochemistry

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Heat

• Energy can also be transferred as heat.

• Heat flows from warmer objects to cooler objects.

Thermochemistry

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We can now provide a more precise definition of energy:

Energy is the capacity to do work or transfer heat.

Thermochemistry

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Conversion of Energy

• Energy can be converted from one type to another.

• For example, the cyclist above has potential energy as she sits on top of the hill.

Thermochemistry

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Conversion of Energy

• As she coasts down the hill, her potential energy is converted to kinetic energy.

• At the bottom, all the potential energy she had at the top of the hill is now kinetic energy.

Thermochemistry

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First Law of Thermodynamics• Energy is neither created nor destroyed.• In other words, the total energy of the universe is

a constant; if the system loses energy, it must be gained by the surroundings, and vice versa.

Thermochemistry

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Internal EnergyThe internal energy of a system is the sum of all kinetic and potential energies of all components of the system; we call it E.

Thermochemistry

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Internal EnergyBy definition, the change in internal energy, E, is the final energy of the system minus the initial energy of the system:

E = Efinal − Einitial

Thermochemistry

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Changes in Internal Energy

• If E > 0, Efinal > Einitial

– Therefore, the system absorbed energy from the surroundings.

– This energy change is called endergonic.

Thermochemistry

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Changes in Internal Energy

• If E < 0, Efinal < Einitial

– Therefore, the system released energy to the surroundings.

– This energy change is called exergonic.

Thermochemistry

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Changes in Internal Energy

• When energy is exchanged between the system and the surroundings, it is exchanged as either heat (q) or work (w).

• That is, E = q + w.

Thermochemistry

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E, q, w, and Their Signs

Thermochemistry

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Exchange of Heat between System and Surroundings

• When heat is absorbed by the system from the surroundings, the process is endothermic.

Thermochemistry

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Exchange of Heat between System and Surroundings

• When heat is absorbed by the system from the surroundings, the process is endothermic.

• When heat is released by the system into the surroundings, the process is exothermic.

Thermochemistry

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State Functions

Usually we have no way of knowing the internal energy of a system; finding that value is simply too complex problem.

Thermochemistry

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State Functions• However, we do know that the internal energy

of a system is independent of the path by which the system achieved that state.– In the system below, the water could have reached

room temperature from either direction.

Thermochemistry

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State Functions• Therefore, internal energy is a state function.• It depends only on the present state of the system, not on

the path by which the system arrived at that state.

• And so, E depends only on Einitial and Efinal.

• The value of state function does not depend on the particular history of the sample, only on its present condition.

Thermochemistry

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State Functions

• However, q and w are not state functions.

• Whether the battery is shorted out or is discharged by running the fan, its E is the same.– But q and w are different

in the two cases.

a) A battery shorted out by a wire loses energy to the surroundings as heat; no work is performed.b) A battery discharged through a motor loses energy as work(to make the fan turn|). Some heat will be released to the surroundings.

Thermochemistry

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Work

Usually in an open container the only work done is by a gas pushing on the surroundings (or by the surroundings pushing on the gas).

Thermochemistry

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WorkWe can measure the work done by the gas if the reaction is done in a vessel that has been fitted with a piston.

w = -PV

Thermochemistry

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Enthalpy• If a process takes place at constant

pressure (as the majority of processes we study do) and the only work done is this pressure-volume work, we can account for heat flow during the process by measuring the enthalpy of the system.

• Enthalpy is the internal energy plus the product of pressure and volume:

H = E + PV

Enthalpy is a state function

Thermochemistry

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Enthalpy

• When the system changes at constant pressure, the change in enthalpy, H, is

H = (E + PV)

• This can be written

H = E + PV

Thermochemistry

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Enthalpy• Since E = q + w and w = -PV, we can

substitute these into the enthalpy expression:

H = E + PV

H = (q+w) − w

H = q• So, at constant pressure, the change in

enthalpy is the heat gained or lost by the system when the process occurs under constant pressure.

H = Hfinal – Hinitial = qp

Thermochemistry

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Endothermicity and Exothermicity

• A process is endothermic when H is positive.

Thermochemistry

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Endothermicity and Exothermicity

• A process is endothermic when H is positive.

• A process is exothermic when H is negative.

Thermochemistry

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Enthalpy of Reaction

The change in enthalpy, H, is the enthalpy of the products minus the enthalpy of the reactants:

H = Hproducts − Hreactants

- It is found experimentally that 890 kJ of heat is produced when1 mol of CH4 is burned in a constant-pressure system.-The combustion of 2 mol of CH4 with 4 mol of O2 -releases twice as much heat, 1780 kJ.

Thermochemistry

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Enthalpy of ReactionThis quantity, H, is called the enthalpy of reaction, or the heat of reaction.

Fig. a)A candle is held near a balloon filled with H2 gas and O2 gas.b) The H2 (g) ignites, reacting with O2 (g) to form H2O (g). The resultant explosion produces the yellow ball of flame. The system gives off heat to its surroundings.c) The enthalpy diagram of this reaction.

(a) (b) (c)

Thermochemistry

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The Truth about Enthalpy

1. Enthalpy is an extensive property.

2. H for a reaction in the forward direction is equal in size, but opposite in sign, to H for the reverse reaction.

3. H for a reaction depends on the state of the products and the state of the reactants.

Thermochemistry

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Calorimetry

Since we cannot know the exact enthalpy of the reactants and products, we measure H through calorimetry, the measurement of heat flow by measuring the temperature change it produces.

Calorimeter

Thermochemistry

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Heat Capacity and Specific Heat

The amount of energy required to raise the temperature of a substance by 1 K (1C) is its heat capacity.

Thermochemistry

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Heat Capacity and Specific Heat

We define specific heat capacity (or simply specific heat) as the amount of energy required to raise the temperature of 1 g of a substance by 1 K.

Thermochemistry

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Heat Capacity and Specific Heat

So if we known (q) we can calculate specific heat:

Cs =q

m T

The amount of heat (q) transferred (gained or loosed) by a masse (m) of substance with a specific heat capacity (Cs) and temperature change of T is:

q = Cs x m x T

The molar heat capacity (Cm) of a substance is:

Cm = Cs x M

M: molar mass of the substance (g/mol)

Thermochemistry

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Constant Pressure Calorimetry-By carrying out a reaction in aqueous solution in a simple calorimeter such as this one, one can indirectly measure the heat change for the system by measuring the heat change for the water in the calorimeter.

• -This calorimeter is used for the reactions occurring in solution.

- Because the calorimeter is not sealed, the reaction occurs under atmospheric pressure.

Fig. Coffee-cup calorimeter, in which reactions occur at constant pressure.

Thermochemistry

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Constant Pressure Calorimetry

Because the specific heat for water is well known (4.184 J/g-K), we can measure H for the reaction with this equation:

qsoln = m Cs T

qsoln = - qrxn

qsoln : the heat gained (loosed) by the solutionqrxn : the heat gained (loosed) by the reactionm : masse of solutionCs : specific heat of solution ( 4.184 J/g-K)

Thermochemistry

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Bomb Calorimetry• Reactions can be carried out in a

sealed “bomb” such as this one.• The heat absorbed (or released) by

the water is a very good approximation of the enthalpy change for the reaction.

• Combustion reactions are the most conveniently studied using bomb calorimeter.

• After the sample (organic compound) has been placed in the bomb, the bomb is sealed and pressurized with oxygen.

Fig. Cutaway view of a bomb calorimeter, in witch reactions occur at constant volume.

Thermochemistry

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Bomb Calorimetry• Combustion reactions are the most

conveniently studied using bomb calorimeter.

• After the sample (organic compound) has been placed in the bomb, the bomb is sealed and pressurized with oxygen.

• It is then placed in the calorimeter, which is essentially an insulated container, and covered with an accurately measured quantity of water.

• When all the components within the calorimeter have come to the same temperature, the combustion reaction is initiated by passing an electrical current through a fine wire that is in contact with the sample.

• When the wire gets sufficiently hot,

the sample ignites.

Fig. Cutaway view of a bomb calorimeter, in witch reactions occur at constant volume.

Thermochemistry

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Bomb Calorimetry• Because the volume in the bomb calorimeter is

constant, what is measured is really the change in internal energy, E, not H.

• For most reactions, the difference is very small.• So the heat of the reaction (q rxn) is :

• Ccal : Heat capacity of the calorimeter T:the temperature change of calorimeterq rxn = - Ccal x T

Thermochemistry

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Hess’s Law

H is well known for many reactions, and it is inconvenient to measure H for every reaction in which we are interested.

• However, we can estimate H using published H values and the properties of enthalpy.

Thermochemistry

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Hess’s Law

Hess’s law states that “if a reaction is carried out in a series of steps, H for the overall reaction will be equal to the sum of the enthalpy changes for the individual steps.”

Thermochemistry

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Hess’s Law

Because H is a state function, the total enthalpy change depends only on the initial state of the reactants and the final state of the products.

Thermochemistry

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Enthalpies of Formation

An enthalpy of formation, Hf, is defined as the enthalpy change for the reaction in which a compound is made from its constituent elements in their elemental forms.

2C (graphite) + 3H2(g) + ½ O2 (g) C2H5OH (l) fH = -277.7 kJ

Thermochemistry

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Thermochemistry

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Standard Enthalpies of FormationStandard enthalpies of formation, Hf°, are measured under standard conditions (25 °C and 1.00 atm pressure).

By definition, the standard enthalpy of formation of the most stable form of any element is zero (Hf (O2g) = 0, …)

Thermochemistry

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Calculation of H of reaction using enthalpies of formation

• Imagine this as occurringin three steps:

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

C3H8 (g) 3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

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Calculation of H

• Imagine this as occurringin three steps:

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

C3H8 (g) 3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

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Calculation of H

• Imagine this as occurringin three steps:

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

C3H8 (g) 3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

Thermochemistry

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C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

C3H8 (g) 3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g) 3 CO2 (g)

4 H2 (g) + 2 O2 (g) 4 H2O (l)

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Calculation of H

• The sum of these equations is:

H1 = -Hf°(C3H8(g)),H2 = 3Hf°(CO2(g)),H3 = 4Hf°(H2O(l)),Hrxn = H1 +H2 + H3 = 2220 kJ

Thermochemistry

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Calculation of H

We can use Hess’s law in this way:

H = nHf°products – mHf° reactants

where n and m are the stoichiometric coefficients.

Thermochemistry

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H = [3(-393.5 kJ) + 4(-285.8 kJ)] – [1(-103.85 kJ) + 5(0 kJ)]

= [(-1180.5 kJ) + (-1143.2 kJ)] – [(-103.85 kJ) + (0 kJ)]= (-2323.7 kJ) – (-103.85 kJ) = -2219.9 kJ

C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Calculation of H