Thermodynamics

Youll Need to Know

the definition of energy and it different forms what are the units in which energy can be expressed the difference between temperature and heat what constitutes a system vs. the surroundings what are state functions what constitutes standard state what are the Laws of Thermodynamics: First Law Second Law Third Law what is enthalpy and how is it measured the difference between endothermic and exothermic how to calculate problems involving enthalpy what is Hesss Law and how to solve problems involving it what is heat of formation and how to solve problems involving it what is specific heat and how to solve problems involving it what is heat capacity and how to solve problems involving it what is calorimetry (both constant volume and constant pressure) and how to solve problems involving it what is entropy and how to solve problems involving it what is Gibbs Free Energy and how to solve problems involving it how to draw and interpret energy diagrams what catalysts are, how they function and how they affect energy diagrams

Energy
Energy is the capacity to do work. Two forms of energy important in chemistry are: (1) thermal energy, which is energy associated with the random motion of atoms and molecules and can be calculated from temperature measurements and (2) chemical energy, which is energy stored within the molecules and can be determined by the type and arrangement of atoms in a substance. Energy is usually expressed in kilojoules (kJ).

Thermodynamics

Temperature vs. Heat

Temperature is the measure of the average kinetic energy of the particles in a sample of matterexpressed in degrees. Heat is the transfer of thermal energy between two objects that are at different temperatures. Heat flows from hotter objects to colder objects. The study of heat that involves chemical reactions is called thermochemistry. A cup of boiling water at 100C has a higher temperature than a swimming pool of water at 20C; but, the water in the swimming pool would have more total thermal energy and, likewise, more heat content.

A System vs. Surroundings

A system involves just the substances involved in chemical and physical changes; everything else outside the system is known as the surroundings. There are three types of systems: (1) open, which can exchange mass and heat energy with the surroundings; (2) closed, only heat energy (not mass) is allowed to be transferred to the surroundings; and (3) isolated, neither mass nor energy is transferred to the surroundings.

State Functions
The values of state functions (e.g., H, G, S) are fixed when temperature, pressure, composition, and physical form are specified. They depend ONLY on the change between the initial and final state of a system and do not depend on the process by which the change occurred; they are independent of the reaction pathway.

Standard State
If you see a following a symbol (example: H or G) it means conditions are standard state. Standard state conditions are: all gases are at 1 atm pressure; all solids and liquids are pure; all solutions are 1-molar (1M) in concentration; and the temperature is 298K (25C).

Laws of Thermodynamics

The First Law of Thermodynamics is, the total quantity of energy in the universe is assumed to remain constant. Energy cannot be created nor destroyed, it can only be converted from one form to another. The Second Law of Thermodynamics says, reactions that are spontaneous must lead to an increase in the entropy of the universe (Suniv > 0). Reactions that are spontaneous in one direction cannot be spontaneous in the opposite direction (you cant have it both ways). The Third Law of Thermodynamics is the entropy of a perfect crystal at 0K is zero; this allows us to calculate the entropy of any substance.

Enthalpy
The change in enthalpy for a reaction (H) is the overall measure of the energy that is absorbed to break bonds and the energy released when bonds form. A reaction is said to be spontaneous if it occurs without being driven by some outside force. There are two driving forces for all chemical reactions: enthalpy and entropy. H = H(products) H(reactants)

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Exothermic (H) gives off heat (favors spontaneous reactions) Endothermic (+H) absorbs heat (favors non-spontaneous reactions)

Products have stronger bonds (lower enthalpy) than reactants. Products have weaker bonds (higher enthalpy) than reactants.

Products are more stable than reactants. Products are less stable than reactants.

Hesss Law
If you can break a chemical reaction up into a series of steps, just add up all the Hs for each step to get the overall H for the reaction. 1. Write the overall equation for the reaction if not given. 2. Manipulate the given equations for the steps of the reaction so they add up to the overall equation. If you reverse an equation, reverse the sign of H. If you multiply equations to obtain a correct coefficient, you must also multiply the H by this coefficient. 3. Add up the equations canceling common substances in reactant and product. 4. Add up all the heats of the steps.

Example
Q. Calculate the heat of combustion of methane into gaseous H2O given the information below: 2O (g) " O 2 (g) 2H (g) + O (g) " H 2 O (g) C (graphite) + 2O (g) " CO 2 (g) C (graphite) + 2H 2 (g) " CH 4 (g) 2H (g) " H 2 (g) A. B. C. D. E. A. D. CH 4 (g) " C (graphite) + 2H 2 (g) Hc = + 75 kJ/mol* C + 2O (g) " CO 2 (g) Hc = - 643 kJ/mol* 2O 2 (g) " 4O (g) Hc = 498 kJ/mol* 4H (g) + 2O (g) " 2H 2 O (g) Hc = -1606 kJ/mol* 2H 2 (g) " 4H (g) Hc = 872 kJ/mol* ______________________________________________________ CH 4 (g) + 2O 2 (g) " CO 2 (g) + 2H 2 O (g) Hc = - 804 kJ/mol
(graphite)

Hc = - 249 kJ/mol Hc = - 803 kJ/mol Hc = - 643 kJ/mol Hc = - 75 kJ/mol Hc = - 436 kJ/mol

100. kJ/mol 201 kJ/mol 402 kJ/mol 804 kJ/mol +804 kJ/mol

* Remember to reverse the sign of H if the reaction is reversed. Also remember to multiply the value of H if necessary. For example, for 2O2(g) 4O(g), the reaction was reversed so the sign of H was changed from negative to positive AND the equation was doubled, therefore the value of H was likewise doubled.

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Thermodynamics

Heat of Formation (H f)
The heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm. By convention, the standard enthalpy of formation for any element in its most stable form is 0.

Example
Q. The heat of formation of CO2(g) and H2O(l) are 394 kJ/mole and 285.8 kJ/mole, respectively. Using the data for the following combustion reaction, calculate the heat of formation of C3H4(g). C3H4(g) + 4O2(g) 3CO2(g) + 2H2O(l) H = 1939.1 kJ

A. To solve this problem, use Hesss Law and reverse the reaction above to make C3H4(g) a product (remember to reverse the sign) and then add together the reactions for the heat of formation of CO2(g) and H2O(l), remembering that the intermediates (H2O, O2, and CO2) need to be eliminated so that all that ends up on the right side is C3H4(g). 3CO 2 (g) + 2H 2 O (l) " C 3 H 4 (g) + 4O 2 (g) H 1 = +1939.1 kJ

3C (s) + 3O 2 (g) " 3CO 2 (g) Hc f = 3 ^ - 394 kJ/molh 1 m O " 2H O 2H 2 (g) + 2 c Hc f = 2 ^ - 285.8 kJ/molh 2 (g) 2 (l) 2 ________________________________________________________ 3C (s) + 2H 2 (g) " C 3 H 4 (g) Hc f = 185.5 kJ/mole

Specific Heat and Heat Capacity

Specific heat (c) is the amount of heat required to raise the temperature of 1 gram of a substance by 1C; the units are J g1 C1. Heat capacity (Cp for constant pressure, Cv for constant volume) is the amount of heat required to raise the temperature of a given quantity (m) of substance by 1C and is measured in J C1. q represents the amount of heat released or absorbed and is measured in kJ (negative = exothermic, positive = endothermic). Cp= m $ c C p = H T where T = T final - T initial q = m $ c $ T q = C p $ T

Examples
Q. 100. grams of water is heated from 20C to 30C. The specific heat of water is 4.184 J g1 C1. Calculate the amount of heat absorbed by the water. A. q = m c T = (100. g) (4.184 J g1 C1) (30.0C 20.0C) = 4.18 103 J = 4.18 kJ

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Q. 100. grams of aluminum foil at 20.0C is placed in contact with 10.0 grams of iron foil at 60.0C. The specific heat of aluminum is 0.900 J g1 C1 and the specific heat of iron is 0.444 J g1 C1. Assuming that no heat is lost to the surroundings, what is the final temperature of the combined metals? A. According to the Law of Conservation of Energy, the heat gained by the aluminum will be equal to the heat lost by the iron (heat flows from warmer objects to cooler objects): qAl = qFe. qAl = m c T = (100. g) (0.900 J g1 C1) (Tf 20.0C) qFe = m c T = (10.0 g) (0.444 J g1 C1) (Tf 60.0C) (100. g) (0.900 J g1 C1) (Tf 20.0C) = (10.0 g) (0.444 J g1 C1) (Tf 60.0C) Tf = 17.9C

Calorimetry
A coffee-cup calorimeter (see diagram below) can be used to determine heats of reactions for neutralization reactions and heats of dilution. The coffee cup is not sealed so the pressure is constant atmospheric air pressure. Furthermore, since the measurements are carried out at constant atmospheric pressure, qrxn = H. qrxn = H qrxn = (qsoln + qcalorimeter) qcalorimeter = Ccalorimeter T

Glass stirring rod

Thermometer Styrofoam cover

400 ml beaker

Polystyrene cups Water

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Example
Q. 100. mL of a 1.00 M HCl solution was mixed with 100. mL of 2.00 M NaOH in a coffee-cup calorimeter. The coffee-cup calorimeter had a heat capacity of 500. J/C. The temperatures of both the HCl and the NaOH solutions were initially both 30.0C and at the end of the experiment, the final temperature reached was 40.0C. Assume the densities and specific heats of both the HCl and the NaOH solutions were the same as the values for water (1.00 g/mL for density and 4.184 J g1 C1 for specific heat). Calculate the heat of neutralization for the reaction. A. qrxn = (qsoln + qcalorimeter) The limiting reactant is HCl (there are less moles of H+ (0.100 L) (1.00 M HCl) = 0.100 mols than OH (0.100 L) (2.00 M NaOH) = 0.200 mols). 100. mL 1.00 g/mL = 100. g qsoln = m c T = (100. g + 100. g) (4.184 J g1 C1) (40.0C 30.0C) = 8.37 103 J qcalorimeter = Ccalorimeter T = (500. J/C ) (10.0C) = 5.00 103 J qrxn = (qsoln + qcalorimeter) = (8.37 103 J + 5.00 103 J) = 1.34 104 J = 13.4 kJ q neutralization= -13.4 kJ =- 134 kJ/molHCl reacted 0.100 molesH +

Entropy (S)
Entropy is a measure of the randomness or disorder of a system. The greater the disorder, the greater the entropy (e.g., dust in the air would have a higher entropy than atoms arranged in a crystal lattice). In terms of entropy: (1) gases have higher entropy than liquids and liquids have higher entropy than solids (g > l > s); (2) when a pure solid or liquid dissolves in a solvent, the entropy of the substance increases; (3) when a gas molecule escapes from a solvent, there is an increase in entropy; (4) entropy generally increases with increasing molecular complexity; and (5) reactions that increase the number of moles of particles often increase the entropy of the system. S = Sproducts Sreactants

Examples
Q. Consider the following reactions and predict whether the entropy change (S) is positive or negative. (a) Na+(aq) + Cl(aq) NaCl(s) (b) NH4Cl(s) NH3(g) + HCl(g) (c) 2NH3(g) + CO2(g) NH2CONH2(aq) + H2O(l) (d) C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(g) A. (a) S is negative. The Na+(aq) and Cl(aq) ions are free to move in solution. NaCl(s) is a solid and the particles are held in a crystal lattice. Furthermore, there are two particles on the reactant side and only one particle on the product side. (b) S is positive. The reaction proceeds from an orderly solid state to a disordered gaseous state. (c) S is negative. The initial reactants are gases (disorder) and the product are solution and liquid (more order). (d) S is positive. The number of total moles of gas for the final products is greater than the reactants.

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Q. Using the values below, calculate the standard entropy change (Srxn) that occurs when methane combusts in oxygen gas to form carbon dioxide and water.
Substance CH4(g) O2(g) CO2(g) H2O(l) S (J K1 mol1) 186.19 205.0 213.6 69.9

A. CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Sc rxn = Sc products - Sc reactants = ` Sc CO + 2Sc H O j - ` Sc CH + 2Sc O j

2 2 4 2

= : 213.6 + 2 ^ 69.9h - `186.19 + 2 ^ 205.0 hj D = - 242.8 J $ K - 1

Gibbs Free Energy (G)

Gibbs free energy is the energy associated with a chemical reaction that can be used to do work. It can be used to determine if a reaction is spontaneous or not. Pure elements at standard conditions are assigned a Gf = 0. If G < 0, the reaction is spontaneous in the forward direction. If G = 0, the reaction is at equilibrium (this will be reviewed in Chapter 10, Equilibrium). If G > 0, then the reaction is nonspontaneous in the forward direction, but the reverse reaction will be spontaneous. The relationship G = G + RT ln K will be also be discussed in more detail in Chapter 10. G = Gf (products) Gf(reactants) G = H TS (standard state) G = H TS (non-standard state) G = G + RT ln K
H exothermic S + products more disordered products less disordered G spontaneous at all T

TS favors spontaneity + opposes spontaneity

exothermic

() spontaneous at low T (+) non-spontaneous at high T Enthalpically-driven process (+) non-spontaneous at low T () spontaneous at high T Entropically-driven process + non-spontaneous at all T

+ endothermic

+ products more disordered

favors spontaneity

+ endothermic

products less disordered

+ opposes spontaneity

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Examples
Q. Ammonium nitrate dissolves in water to form ammonium and nitrate ions. Given the following information at standard conditions, calculate H, S, and G and determine if the reaction is spontaneous or not. A. NH4NO3(s) NH4+(aq) + NO3(aq)
Compound NH4NO3(s) NH
+ 4 (aq)

Hf (kJ mol1) 366 133 205

S (J mol 1 K 1) 151 113 146

NO3(aq)

H = Hf(products) Hf(reactants) H = [(133 kJ) + (205 kJ)] (366 kJ) = 28 kJ S = S(products) S(reactants) S = (113 J K1 + 146 J K1) 151 J K1 S = 108 J K1 = 0.108 kJ K1 T = 25C + 273 = 298K G = H TS = 28 kJ 298K(0.108 kJ K1) = 4 kJ since G < 0, the reaction is spontaneous. Q. Calculate G at 298K for the Haber reaction starting with 1.0 atm N2(g), 3.0 atm H2(g), and 1.0 atm NH3(g). G = 33.3 kJ A. N2(g) + 3H2(g) @ 2NH3(g) G = G + RT ln K K = 1.02 / (1.0 3.03) K = 3.7 102 G = 33.3 kJ + [8.314 J/K 298K ln (3.7 102)] G = 33.3 kJ 8.17 kJ = 41.5 kJ The results follow Le Chateliers principle: Adding more H2(g) would drive the reaction to the right. * At standard conditions the pressure of all components is 1 atm. We use G in this case because not all pressures are 1 atm.

Energy Diagrams
Only a very small fraction of collisions that occur result in a reaction because: (1) The colliding molecules must be oriented in exactly the correct way for the product molecule bonds to be formed, and (2) the two molecules must collide with sufficient energy to overcome the activation energy of the reaction. The activation energy (Ea) is defined as the minimum energy needed to initiate a chemical reaction.

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Energy

Ea

Products

Reactants Reaction Coordinate

Endothermic
(The energy of the products is less than the energy of the reactants.)

Catalyst Added
transition state (uncatalyzed) activation energy (uncatalyzed)

transition state (catalyzed)

reagents activation energy (catalyzed)

H

products

Because the catalyzed activation energy is lower than the uncatalyzed activation energy, this reaction will take place more quickly. Keep in mind, though, that the transition state is totally different for the catalyzed reaction.

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