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Chapter 6 Thermochemistry

Chemistry: A Molecular Approach, 2nd Ed. Nivaldo Tro

Energy
The ability to do work or transfer heat.
 Work: Energy used to cause an object that has mass to move.  Heat: Energy used to cause the temperature of an object to rise.
Heat is the flow of energy caused by a difference in temperature.

Energy, Heat, and Work


You can think of energy as a quantity an object can possess
or collection of objects

You can think of heat and work as the two different ways that an object can exchange energy with other objects
either out of it, or into it

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

Kinetic Energy
Energy an object possesses by virtue of its motion. 1 KE = mv2 2

Units of Energy
The SI unit of energy is the joule (J). kg m2 1 J = 1 s2 An older, non-SI unit is still in widespread use: The calorie (cal). 1 cal = 4.184 J

Some Forms of Energy


Electrical
 kinetic energy associated with the flow of electrical charge

Heat or thermal energy


 kinetic energy associated with molecular motion

Light or radiant energy


 kinetic energy associated with energy transitions in an atom

Nuclear
 potential energy in the nucleus of atoms

Chemical
 potential energy due to the structure of the atoms, the attachment between atoms, the atoms positions relative to each other in the molecule, or the molecules, relative positions in the structure

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).

Work
Energy used to move an object over some distance. w = F  d, where w is work, F is the force, and d is the distance over which the force is exerted.

Heat
Energy can also be transferred as heat. Heat flows from warmer objects to cooler objects.

Transferal of Energy
a) The potential energy of this ball of clay is increased when it is moved from the ground to the top of the wall.

Transferal of Energy
a) The potential energy of this ball of clay is increased when it is moved from the ground to the top of the wall. b) As the ball falls, its potential energy is converted to kinetic energy.

Transferal of Energy
a) The potential energy of this ball of clay is increased when it is moved from the ground to the top of the wall. b) As the ball falls, its potential energy is converted to kinetic energy. c) When it hits the ground, its kinetic energy falls to zero (since it is no longer moving); some of the energy does work on the ball, the rest is dissipated as heat.

First Law of Thermodynamics


The Law of Conservation of Energy states that energy cannot be 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.

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

Use Fig. 5.5

Internal Energy
By definition, the change in internal energy, (E, is the final energy of the system minus the initial energy of the system: (E = Efinal Einitial

Use Fig. 5.5

Changes in Internal Energy


If (E > 0, Efinal > Einitial
Therefore, the system absorbed energy from the surroundings. This energy change is called endergonic.

Changes in Internal Energy


If (E < 0, Efinal < Einitial
Therefore, the system released energy to the surroundings. This energy change is called exergonic.

Changes in Internal Energy


Energy is exchanged between the system and surroundings through heat (q) and work (w) That is, (E = q + w.

(E, q, w, and Their Signs


(E = q + w

If the reaction produces 3.1 x 102 J of heat and the decrease in volume requires the surroundings do 7.6 J of work on the gases, what is the change in internal energy of the gases?
Given: Find: Concept Plan:

qreaction = 310 J, wsurroundings = 7.6 J (Egases, J


w surrounding w gases q, w
(E

Relationships: q system = qsurroundings, wsystem = wsurroundings, (E = q + w Solution:

Check:

the units are correct, the sign is reasonable as the amount of heat lost in the reaction is much larger than the amount of work energy gained

Exchange of Heat between System and Surroundings


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

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 to the surroundings, the process is exothermic.

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

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.

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.

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.

Pressure Volume Work


When a process occurs in an open container, commonly the only work done is a change in volume of a gas pushing on the surroundings (or being pushed on by the surroundings).

Work
We can measure the work done by the gas if the reaction is done in a vessel that has been fitted with a piston. w = P(V

Practice A certain process results in a gas system releasing 68.3 kJ of energy. During the process, 15.8 kcal of heat is released by the system. If the external pressure is kept constant at 1.00 atm and the initial volume of the gas is 10.0 L, what is the final volume of the gas?
Given: Find: Conceptual Plan:

(E = 68.3 kJ, q1015.8 kcal, V1 = 10.0104J, V = atm (E = 6.83 x = 4 J, q = 6.604 x L, P = 1.00 10.0L,
1

P L V2,= 1.00 atm V2, L q, (E w V2 P, V1

Relationships: (E = q + w, w = P(V, 1 kJ = 1000 J, 1 cal = 4.18 J, 101.3 J = 1 atmL Solution:

Check:

so both (E and q are , and (E > q, w must be ; and when w is the system is expanding, so V2 should be greater than V1; and it is

Enthalpy
Enthalpy is the internal energy plus the product of pressure and volume: H = E + PV When the system changes at constant pressure, the change in enthalpy, (H, is (H = ((E + PV) (H = (E + P(V

Enthalpy
Since (E = q + w and w = P(V, we can substitute these into the enthalpy expression: (H = (E + P(V (H = (qp+w) w (H = qp So, at constant pressure the change in enthalpy is the heat gained or lost.

Enthalpy
Usually (H and (E are similar in value, the difference is largest for reactions that produce or use large quantities of gas

Endothermicity and Exothermicity


A process is endothermic, then, when (H is positive.

Endothermicity and Exothermicity


A process is endothermic when (H is positive. A process is exothermic when (H is negative.

Enthalpies of Reaction
The change in enthalpy, (H, is the enthalpy of the products minus the enthalpy of the reactants: (H = Hproducts Hreactants

Enthalpies of Reaction
This quantity, (H, is called the enthalpy of reaction, or the heat of reaction.

Enthalpy of Reaction
The enthalpy change in a chemical reaction is an extensive property
 the more reactants you use, the larger the enthalpy change

By convention, we calculate the enthalpy change for the number of moles of reactants in the reaction as written
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g) (H = 2044 kJ

Example 6.7: How much heat is evolved in the complete combustion of 13.2 kg of C3H8(g)?
Given: Find: Conceptual Plan:

13.2 kg C3H8, q, kJ/mol

kg

mol

kJ

Relationships: Solution:

1 kg = 1000 g, for 1 mol C3H8 (Hrxn= 2044 kJ, Molar Mass = 44.09 g/mol

Check:

the sign is correct and the number is reasonable because the amount of C3H8 is much more than 1 mole

The Truth about Enthalpy


1. Enthalpy is an extensive property.
When reaction is multiplied by a factor, (Hrxn is multiplied by that factor

C(s) + O2(g)

CO2(g)

(H = 393.5 kJ

2 C(s) + 2 O2(g)

2 CO2(g) (H = 2(393.5 kJ) = 787.0 kJ

The Truth about Enthalpy


2. (H for a reaction in the forward direction is equal in size, but opposite in sign, to (H for the reverse reaction. C(s) + O2(g) CO2(g) CO2(g) (H = 393.5 kJ (H = +393.5 kJ

C(s) + O2(g)

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

Calorimetry
Since we cannot know the exact internal energy and enthalpy of the reactants and products, we measure through calorimetry, the measurement of heat flow.

Heat Capacity and Specific Heat


The amount of energy required to raise the temperature of a substance by 1 K (1rC) is its heat capacity.
The molar heat capacity is the amount of energy required to raise the temperature of one mole of a substance 1rC We define specific heat capacity (or simply specific heat) as the amount of energy required to raise the temperature of one gram of a substance by 1 K.

Heat Capacity and Specific Heat


Specific heat, then, is heat transferred Specific heat = mass v temperature change q C= m v (T

Practice Calculate the amount of heat released when 7.40 g of water cools from 49r to 29 rC
Given: Find: Conceptual Plan:

T1= 49 rC, T2 = 29 rC, m = 7.40 g q, J

Cs m, (T
q = m Cs (T Cs = 4.18 J/grC (Table 6.4)

Relationships: Solution:

Check:

the unit is correct, the sign is reasonable as the water must release heat to make its temperature fall

Constant Pressure Calorimetry


(Measuring (H)
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.

Constant Pressure Calorimetry


Because the specific heat for water is well known (4.184 J/mol-K), we can measure (H for the reaction with this equation: q = m v C v (T

qreaction =

qsolution

= (masssolution x Cs, solution x (T) (Hreaction = qconstant pressure = qreaction


to get (Hreaction per mol, divide by the number of moles

Practice What will be the final temperature of the solution in a coffee cup calorimeter if a 50.00 mL sample of 0.250 M HCl(aq) is added to a 50.00 mL sample of 0.250 NaOH(aq). The initial temperature is 19.50 rC.
((H =57.2 kJ/mol, Cs = 4.18 J/goC and d = 1.00 g/mL)

Given: 50.00 mL of 0.250 M HCl, 50.00 mL of 0.250 M NaOH 1 L solution d = 1.00 g/mL, Cs = 4.18 J/goC, (H = 57.2 kJ/mol T1 = 19.50 o C, Find: T2, o C Conceptual qsoln Cs, qsoln, m (H qrxn (T T2 Plan: Relationships: Solution:
qsln = m x Cs,sln x (T = qrxn ; mol of OH- or H+ = M*V = 0.250M *50x10-3L=1.25x10-2 moles Total volume of sln is 1 L m = d*v = 100 g 1.25x10-2 moles

H+

OH1.25x10-2

1.25x10-2

H2O

Check: the sign is correct and the value is reasonable, because the reaction is
exothermic we expect the final temperature to be higher than the initial

Bomb Calorimetry
(Measures (E)
Used to measure (E because it is a constant volume system The heat capacity of the calorimeter is the amount of heat absorbed by the calorimeter for each degree rise in temperature and is called the calorimeter constant
 Ccal, kJ/C

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.

Practice When 1.22 g of HC7H5O2 is burned in a bomb calorimeter, the temperature rises from 20.27 rC to 22.67 rC. If (E for the reaction is 3.23 x 103 kJ/mol, what is the heat capacity of the calorimeter in kJ/rC?
1.22 g 103 mol T1=20.27 (T T =22.67 (E= 3.23 x 10 kJ/mol Given: 9.990 xHC7H5O2, HC7H5O2, rC, = 22.40 rC,rC, (E= 3.23 x 3103 kJ/mol

Find: Ccal, kJ/rC Conceptual Plan:

mol, (E

qrxn

qcal

qcal, (T

Ccal

Relationships: Solution:

qcal = Ccal x (T = qrxn MM HC7H5O2 = 122.12 g/mol

Check:

the units and sign are correct

When two objects at different temperatures are placed in contact, heat flows from the material at the higher temperature to the material at the lower temperature Heat flows until both materials reach the same final temperature The amount of heat energy lost by the hot material equals the amount of heat gained by the cold material qhot = qcold mhotCs,hot(Thot = (mcoldCs,cold(Tcold)

Heat Transfer & Final Temperature

A piece of metal at 85 rC is added to water at 25 rC, the final temperature of the both metal and water is 30 rC. Which of the following is true?
1. Heat lost by the metal > heat gained by water 2. Heat gained by water > heat lost by the metal 3. Heat lost by the metal > heat lost by the water 4. Heat lost by the metal = heat gained by water 5. More information is required

Practice A hot piece of metal weighing 350.0 g is heated to 100.0 rC. It is then placed into a coffee cup calorimeter containing 160.0 g of water at 22.4 rC. The water warms and the copper cools until the final temperature is 35.2 rC. Calculate the specific heat of the metal and identify the metal.

Practice Calculate the specific heat and identify the metal from the data
Given: Find: Concept Plan:

metal: 350.0 g, T1 = 100.0 rC, T2 = 35.2 rC H2O: 160.0 g, T1 = 22.4 rC, T2 = 35.2rC, Cs = 4.18 J/g rC m, q Cs , metal, J/gC Cs, (T
q = m x Cs x (T; qmetal = qH2O

Relationships: Solution:

Check:

the units are correct, the number indicates the metal is copper

Hesss 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 (H values that are published and the properties of enthalpy.

Hesss Law
Hesss 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.

Hesss 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.

Practice Hesss Law


Given the following information: Cu(s) + Cl2(g) p CuCl2(s) Cu(s) + Cl2(g) p CuCl(s) (Hr = 206 kJ (Hr = 18 kJ

Calculate the (Hr for the reaction below: Cu(s) + CuCl2(s) p 2 CuCl(s) (Hr = ? kJ CuCl2(s) p Cu(s) + Cl2(g) 2 Cu(s) + Cl2(g) p 2 CuCl(s) Cu(s) + CuCl2(s) p 2 CuCl(s) (Hr = +206 kJ (Hr = 2x(-18) kJ (Hr = +170. kJ

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.

Standard Enthalpies of Formation


r Standard enthalpies of formation, (Hf, are measured under standard conditions (25rC and 1.00 atm pressure).

Formation Reactions
Reactions of elements in their standard state to form 1 mole of a pure compound
if you are not sure what the standard state of an element is, find the form in Appendix IIB that has a (Hfr = 0 because the definition requires 1 mole of compound be made, the coefficients of the reactants may be fractions

Writing the Formation Reaction


(for CO(g))
The formation reaction is the reaction between the elements in the compound. C+O CO(g) The elements must be in their standard state
 there are several forms of solid C, but the one with (Hfr = 0 is graphite  oxygens standard state is the diatomic gas

C(s, graphite) + O2(g) CO(g) The equation must be balanced, but the coefficient of the product compound must be 1 C(s, graphite) + O2(g) CO(g)

Write the formation reactions for the following:


CO2(g) C(s, graphite) + O2(g) p CO2(g)

Al2(SO4)3(s)

2 Al(s) + 3/8 S8(s, rhombic) + 6 O2(g) p Al2(SO4)3(s)

Calculation of (H
C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in 3 steps:
C3H8 (g) p 3 C(graphite) + 4 H2 (g) 3 C(graphite) + 3 O2 (g) p 3 CO2 (g) 4 H2 (g) + 2 O2 (g) p 4 H2O (l)

Calculation of (H
C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in 3 steps:
C3H8 (g) p 3 C(graphite) + 4 H2 (g) 3 C(graphite) + 3 O2 (g) p 3 CO2 (g) 4 H2 (g) + 2 O2 (g) p 4 H2O (l)

Calculation of (H
C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in 3 steps:
C3H8 (g) p 3 C(graphite) + 4 H2 (g) 3 C(graphite) + 3 O2 (g) p 3 CO2 (g) 4 H2 (g) + 2 O2 (g) p 4 H2O (l)

Calculation of (H
C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)
The sum of these equations is:
C3H8 (g) p 3 C(graphite) + 4 H2 (g) 3 C(graphite) + 3 O2 (g) p 3 CO2 (g) 4 H2 (g) + 2 O2 (g) p 4 H2O (l) C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)

Calculation of (H
We can use Hesss law in this way:
r r (H = 7n(Hf(products) - 7m(Hf(reactants)

where n and m are the stoichiometric coefficients.

Calculation of (H
C3H8 (g) + 5 O2 (g) p 3 CO2 (g) + 4 H2O (l)
(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

Example 6.12: How many kg of octane must be combusted to supply 1.0 x 1011 kJ of energy?
Given: Find: Conceptual Plan:

1.0 x 1011 kJ
mass octane, kg
(Hfrs (Hrxnr

(Hrrxn = 5074.1 kJ

Write the balanced equation per mole of octane


kJ
from above

mol C8H18

g C8H18

kg C8H18

Relationships: Solution:

MMoctane = 114.2 g/mol, 1 kg = 1000 g


C8H18(l) + 25/2 O2(g) 8 CO2(g) + 9 H2O(g)

Look up the (Hfr for each material in Appendix IIB the units and sign are correct, the large value is expected

Check:

Renewable Energy
Our greatest unlimited supply of energy is the sun New technologies are being developed to capture the energy of sunlight
parabolic troughs, solar power towers, and dish engines concentrate the suns light to generate electricity solar energy used to decompose water into H2(g) and O2(g); the H2 can then be used by fuel cells to generate electricity
H2(g) + O2(g) H2O(l) (Hrrxn = 285.8 kJ

Hydroelectric power Wind power