Spontaneity

Spontaneous change
A process that occurs in a system left to itself; no outside intervention is necessary to sustain the process E.g.

4 Fe(s) + 3 O2(g) 2 Fe2O3(s)

Nonspontaneous change
A process that will not occur unless some external action is continuously applied.

Spontaneity
A ball rolls down a hill but never spontaneously rolls back up the hill. A gas fills its container uniformly; it never spontaneously collects at one end of the container. Heat flows from a hotter body to a colder one, but the reverse never happens spontaneously. Paper burns spontaneously in an exothermic reaction to form CO2(g) and H2O(l) but paper is not formed when CO2(g) and H2O(l) are heated together.

What happens to the potential energy of the system in each of these examples?

Entropy
BUT! There are also spontaneous reactions that are endothermic: Solid-to-liquid phase transition H2O(s) H2O(l) H = 6.01 kJ Dissolution of NH4NO3 and NaCl in water (remember these?) Exothermicity does not guarantee the spontaneity of a reaction. What factor is being considered when predicting the spontaneity of a reaction??

ENTROPY!

Entropy
What is ENTROPY?
A state of randomness or disorder of a system. All things in the universe progress from a low entropy to high entropy

Entropy
ENTROPY is a thermodynamic function that describes the number of arrangements that are available to a system existing at a given state. It is closely associated with probability. Nature proceeds spontaneously to states having higher probabilities of existing. Consider the possible arrangements of 4 gas molecules in a 2-bulbed container (Figure 1). Microstate a particular configuration of particles that leads to a specific arrangement.
Figure 1. Possible arrangements of 4 gas molecules in a 2-bulbed container.

Entropy

Figure 1. Possible arrangements of 4 gas molecules in a 2-bulbed container.

Figure 2. All possible microstates of 4 gas molecules in a 2-bulbed container.

Entropy
One important conclusion: The probability of occurrence of a particular arrangement (state) depends on the number of ways or configurations (microstates) that lead to that arrangement.

Entropy
Positional Probability
Probability that depends on the number of configurations in space (positional microstates) Can also be seen in different states of matter

This was also seen in the formation of solutions.

Entropy
For each pair, choose which has the higher entropy:
A. Solid CO2 and gaseous CO2 B. N2 gas at 1 atm and N2 gas at 1.0 x 10-2 atm

Predict the sign of S for each of the following processes:

A. Solid sugar is added to water to form a solution B. Iodine vapor condenses on a cold surface to form crystals

Second Law of Thermodynamics

In any spontaneous process, the entropy of the universe increases. The total energy of the universe remains constant but its entropy is increasing. Mathematically, Suniverse = Ssystem + Ssurroundings Suniverse > 0 the entropy of the universe increases and the process is spontaneous in the direction written the process is spontaneous in the opposite direction the process has no tendency to occur and the system is at equilibrium

Suniverse < 0 Suniverse = 0

Entropy and Temperature

Consider the vaporization of 1 mole of H2O(l)
What is the system in this case? What is the sign of Ssystem? What is the sign of Ssurroundings? What is the sign of Suniverse?

At 1 atm and temperatures above 100C, water spontaneously changes from liquid to gas. At 1 atm and temperatures below 100C, the reverse process (condensation) is spontaneous. TEMPERATURE HAS AN EFFECT!

Entropy and Temperature

Entropy changes in the surroundings are primarily determined by heat flow.

The effect of this heat flow is dependent on the temperature. 2 characteristics of Ssurroundings:
The sign of Ssurroundings depends on the direction of heat flow The magnitude of Ssurroundings depends on the temperature

The minus sign in the formula is important!

Entropy and Temperature

In the metallurgy of antimony, one way to recover the pure metal is through the use of iron to reduce antimony in sulfide ores: Sb2S3(s) + 3 Fe(s) 2 Sb(s) + 3 FeS(s) H = -125 kJ Calculate Ssurr for these reaction at 25C.

Note that Ssurr is positive.

Entropy of the System

Ssys = H T

Consider the fusion of 1 mole of ice with H = 6.01 kJ/mole at 25C 6 010 J

Ssys =
298 K Ssys =

= 22.0 J/K
6 010 J 310 K

= -19.4 J/K

Suniv = Ssys + Ssurr Suniv = 22.0 J/K + -19.4 J/K = 2.6 J/K

Entropy of the System

A system is represented by the following reaction: aA + bB cC + dD The standard entropy of reaction is given by Or, in general

Calculate S at 25C for the reaction 2 NiS(s) + 3 O2(g) 2 SO2(g) + 2NiO(s) given the following standard entropy values:

Entropy of the System

If a reaction leads to more gas molecules, what is the sign of S? If a reaction leads to less gas molecules, what is the sign of S? If a reaction involves no net change in the number of gas molecules, what is the sign of S?

Phase Transitions
At the temperature at which a phase transition occurs, the system is at equilibrium and G = 0.

The molar heats of fusion and vaporization of benzene are 10.9 kJ/mol and 31.0 kJ/mol, respectively. Calculate the entropy changes for the solid to liquid and liquid to vapor transitions for benzene. At 1 atm, benzene melts at 5.5C and boils at 80.1C. Sfusion = 39.1 J K-1 mol-1 Svap = 87.8 J K-1 mol-1

Third Law of Thermodynamics

Thermodynamics commonly considers the change () in functions of a system since some of them cannot be measured absolutely. ABSOLUTE ENTROPY VALUES, however, can be assigned. The entropy of a perfect crystalline substance is zero at the absolute zero of temperature. As the temperature increases, the freedom of motion also increases and the entropy of the substance above 0 K is greater than zero. S = Sfinal Sinitial If the absolute zero is taken as the initial state, then S can readily be computed.

Gibbs Free Energy

The second law of thermodynamics states that in a spontaneous reaction, Suniv > 0. Ssys and Ssurr have to be evaluated. Ssurr is a quantity difficult to measure. A different thermodynamic function must be used to create a criterion for spontaneity for a system. This thermodynamic function is called Gibbs free energy, or simply free energy, defined by G = H TS. The change in free energy in going from one state to another (constant T) is G = H TS Two functions can be used in predicting the spontaneity of processes: entropy (for all processes) and free energy (for processes at constant T and P). Josiah Willard Gibbs

Gibbs Free Energy

Free energy is the energy available to do work. If G is negative, the system released usable energy.

Gibbs Free Energy

STANDARD FREE ENERGY CHANGES (G) The standard free energy change of a reaction is the free energy change for a reaction when it occurs under standard state conditions, when reactants in their standard states are converted to products in their standard states.

Just like H, G absolute values cannot be measured and a reference point must be used.

Gibbs Free Energy

Consider the reaction 2 SO2(g) + O2(g) 2 SO3(g) carried out at 25C and 1 atm. Calculate H, S, and G using the following data:

H = -198 kJ S = -187 J/K G = -142 kJ

Gibbs Free Energy

G = -1378 kJ

Gibbs Free Energy

G = -3 kJ Summary of thermodynamic quantities

Chemical Kinetics
Thermodynamics tells the tendency of a process to take place. It cannot tell how fast a reaction takes place. 2 H2(g) + O2(g) 2 H2O(l) The above reaction has a high tendency to occur but the two gas reactants can coexist and never react to form liquid water at 25C. To completely describe a reaction, stoichiometry and thermodynamics are not enough. The rates of reactions and the factors affecting these add to a complete description of different reactions taking place (or not) around us. This is the concern of CHEMICAL KINETICS.

Chemical Kinetics
Consider the following decomposition reaction: 2 NO2(g) 2 NO(g) + O2(g) Reaction rate change in concentration of reactant or product per unit time

Chemical Kinetics

Change can be positive (an increase in the concentration of the products) or negative (a decrease in the concentration of reactants). For convenience, rate is defined to be a positive quantity.

Chemical Kinetics

Rate is negative since the concentration of NO2 decreased. But rate was defined to be positive so the rate is expressed as

Note that the average rate for 50-second intervals is not constant but decreases with time.

Chemical Kinetics
The rate at a specific point in time is the instantaneous rate. This is the slope of the tangent to the curve at that point. At t = 100 seconds,

Chemical Kinetics
The rate of the reaction can also be defined in terms of the products. Always remember that the stoichiometry must be considered in describing the relative rates of the reactants and products. 2 NO2(g) 2 NO(g) + O2(g) Relate the rate of production of NO to the rate of consumption of NO2. Relate the rate of production of NO to the rate of production of O2. At t = 250 seconds,

Chemical Kinetics
As a summary:

For a general reaction:

the rate is given by

Chemical Kinetics
a. How is the rate at which ozone disappears related to the rate at which oxygen appears in the reaction 2 O3(g) 3 O2(g)?

b. If the rate at which O2 appears is 6.0 x 10-5 M at a particular instant, at what rate is O3 disappearing at the same time?

Rate Law
Expresses the relationship of the rate of a reaction to the rate constant and the concentrations of the reactants raised to some powers. For the general reaction the rate law is given as Rate = k[A]x[B]y k proportionality constant x, y order of reactant The overall order of a reaction is given by the sum of the orders of reactants, i.e., for the general rate law above overall order = x + y The concentrations of the products do not appear in the rate law. The values of x and y must be determined by experiment.

Method of Initial Rates

Initial rate the instantaneous rate determined just after the reaction begins (just after t = 0). The idea is to determine the instantaneous rate before the initial concentrations of the reactants have significantly changed. Consider the following reaction carried out in three different experiments:

The rate law for the reaction is Rate = k[NH4+]n[NO2-]m. The values of n and m are dependent on the initial concentrations of NH4+ and NO2-, respectively.

Method of Initial Rates

For experiments 1 and 2, the concentration of NH4+ is constant but the concentration of NO2- varies. This means that the change on the initial rate is due only to the change in the concentration of NO2-.

Thus, m = 1.

Method of Initial Rates

In order to determine the value of n, experiments 2 and 3 are used.

Thus, n = 1. What is the order of the reaction with respect to NH4+? What is the order of the reaction with respect to NO2-? What is the overall order of the reaction? The value of the rate constant, k, can be evaluated by plugging in values from any of the three experiments into the rate law. What is the value of k in this example?

Method of Initial Rates

Reaction Mechanisms
Chemical kinetics also focus on how reactions occur. A reaction mechanism is a proposed series of steps by which a reaction occurs. It is different from a balanced equation in that the latter does not tell us how a reaction occurs. Consider the reaction between nitrogen dioxide and carbon monoxide:

The following is a proposed mechanism for the above reaction:

Reaction Mechanisms
k1 and k2 are rate constants for the individual reactions called elementary steps. Molecularity refers to the number of species that must collide to bring about the reaction

Elementary step a reaction whose rate can be written from its molecularity What can be said about the molecularity of a reaction and its overall order?

Reaction Mechanisms

Adding the two elementary steps gives the overall reaction given above. The proposed mechanism must agree with the experimentally-determined rate law. Which can be determined first for a reaction: the mechanism or the rate law?

Collision Theory
Central idea: molecules must collide to react and after collision, there must be a redistribution of energy that puts enough energy into some bonds to break them (effective collision). Activation energy (Ea) the minimum energy above the average kinetic energy that molecules must bring to their collisions for a reaction to occur.

Collision Theory
Factors affecting reaction rates: 1. Nature of reactants

Highly reactive substances have high energy

Collision Theory
Factors affecting reaction rates: 2. Concentration of reactants

Collision Theory
Factors affecting reaction rates: 3. Temperature

Collision Theory
Factors affecting reaction rates: 3. Temperature Arrhenius proposed the following equation: Number of collisions with Ea = (total collisions)e-Ea/RT
Ea is the activation energy; R is the gas constant in J mol-1 K-1; T is the temperature in K. The fraction of effective collision increases exponentially with temperature This expression gives the number of total effective collisions Experiment, however, has shown that the observed reaction rate is somewhat less than the rate of effective collisions. Why is this so?? The answer lies in molecular orientations.

Collision Theory
Factors affecting reaction rates:

The collision must involve enough energy to produce the reaction. The relative orientation of the reactants must allow the formation of any new bonds necessary to produce the products.

Collision Theory
Factors affecting reaction rates: 4. Particle size and surface area

Collision Theory
Factors affecting reaction rates: 5. Presence of Catalyst
A catalyst is a substance that speeds up a reaction without being consumed itself. It provides an alternative pathway with a lower activation energy.

Collision Theory
Factors affecting reaction rates:
Catalysts are defined according to their state: Heterogeneous Catalysts Catalyst differs in state from the reactants. Commonly, the catalyst is a solid and the reactants can be gas, liquid or aqueous. Catalysis takes place via adsorption. Homogeneous Catalysts Catalyst has the same state as the reactants.

Transition State Theory

The transition state is an unstable transitory combination of reactant molecules that occur at a potential energy maximum.

The transition state is characterized by partially broken and partially formed bonds in the activated complex. The activated complex is a nonisolable species.

Chemical Equilibrium
Chemical equilibrium is described as a dynamic state where the concentrations of the reactants and products remain constant with time.

Equilibrium Constant
For a general reaction the law of mass action which describes the equilibrium condition is given by the equilibrium constant:

Write the equilibrium expression for the following reaction:

Equilibrium Constant

Equilibrium Constant
For a general reaction

If the reaction is reversed, the new equilibrium expression is

If the original reaction is multiplied by a factor n to give the equilibrium expression becomes

Equilibrium Constant
There are an infinite number of ways to combine equilibrium concentrations of reactants and products that will give the same equilibrium constant. Each set of equilibrium concentrations is called an equilibrium position.

Equilibrium Constant
If K > 1, the reaction system will consist mostly of products; the equilibrium lies to the right. If K < 1, the reaction system will consist mostly of reactants and the equilibrium lies to the left of the written equation. K and the time required to reach equilibrium are not related.
The time required depends on the reaction rate which is dependent on the activation energy. K depends on thermodynamic factors such as the difference in energy of reactants and products.

Reaction Quotient, Q
The reaction quotient, Q, is used in determining if the system is at equilibrium and if not, to which direction it will shift to achieve equilibrium. Q is obtained by applying the law of mass action using concentrations at states other than the equilibrium state of the system. It has the same formula as the equilibrium constant, K.

Reaction Quotient, Q
Using the reaction quotient:

Calculating for Equilibrium Concentrations

Sometimes, the initial values of the reactants and products are given instead of equilibrium concentrations. In these cases, an ICE table is very helpful in computing for equilibrium concentrations.

A.

B.

Le Chateliers Principle
There are factors that affect the position of a chemical equilibrium. The effects of these factors (changes in concentration, temperature and pressure) on a system at equilibrium can be qualitatively predicted by using Le Chateliers principle. If a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction that tends to reduce that change.

Henry Louis Le Chatelier

Le Chateliers Principle
1. Effect of Change in Concentration If a component (reactant or product) is added to a reaction system at equilibrium (at constant T and P or constant T and V), the equilibrium position will shift in the direction that lowers the concentration of that component. If a component (reactant or product) is removed from a reaction system at equilibrium (at constant T and P or constant T and V), the equilibrium position will shift in the direction that increases the concentration of that component.

Le Chateliers Principle
2. Effect of Change in Pressure There are 3 ways to change the pressure of a system:
a. Add or remove a gaseous reactant or product b. Add an inert gas (one not involved in the reaction) c. Change the volume of the container

The addition of an inert gas increases the total pressure and changes the partial pressures or concentrations of the reactants or products but the equilibrium constant remains the same. When the volume of the container holding a gaseous system is reduced, the system responds by reducing its own volume. This is done by decreasing the total number of gaseous molecules in the system.

Le Chateliers Principle
2. Effect of Change in Pressure

Le Chateliers Principle
3. Effect of Change in Temperature
The effect of the previous two factors is changing the equilibrium position (equilibrium concentrations) but not the value of K. K depends on temperature

Le Chateliers Principle
3. Effect of Change in Temperature
Treat energy as a reactant (endothermic process) or as a product (exothermic process), and predict the direction of shift in the same way as when an actual reactant or product is added or removed. A temperature increase favors an endothermic reaction, and a temperature decrease favors an exothermic reaction.

Le Chateliers Principle
4. Effect of Catalyst
Adding a catalyst to a reaction mixture that is not yet at equilibrium will simply cause the mixture to reach equilibrium sooner. Kinetics and thermodynamics are independent of each other.

Equilibrium Constant

Free Energy and Chemical Equilibrium

Under conditions that are not standard state, the following equation holds: G = G + RT lnQ
R = 8.314 J mol-1 K-1 T is in Kelvin Q is the reaction quotient

At equilibrium, G = 0 and Q = K, where K is the equilibrium constant. The following equation applies for a reaction system at equilibrium: G = - RT lnK The larger the value of K, the more negative G is and the more spontaneous the process.

Free Energy and Chemical Equilibrium

Acid-Base Equilibria
Acid-Base Properties of Water
Water is an amphoteric substance. It is a weak electrolyte and is a poor conductor of electricity. However, it undergoes dissociation to a small extent: H2O(l) H+(aq) + OH-(aq) 2 H2O(l) H3O+(aq) + OH-(aq) Which are the conjugate acid-base pairs? Autoionization of water The equilibrium constant expression for the autoionization of water is given by

Kc =

[H+][OH-] [H2O]

The concentration of water in aqueous solutions is considered constant.

Kc [H2O] = [H+][OH-]
Kw = [H+][OH-] Kw is the ion-product constant of water at a specific temperature. At 25C, Kw has a value of 1.0 x 10-14.

Acid-Base Equilibria
Calculate the concentration of H+ in (a) a solution in which [OH-] is 0.010 M; (b) a solution in which [OH-] is 1.8 x 10-9 M. (Unless otherwise stated, the temperature is 25C.) (a) Kw = [H+][OH-] (b) Kw = [H+][OH-] Kw 1.0 x 10-14 Kw 1.0 x 10-14 H+ = = H+ = = -] [OH 0.010 [OH-] 1.8 x 10-9 H+ = 1.0 x 10-12 M Is this solution acidic or basic? H+ = 5.6 x 10-6 M Is this solution acidic or basic?

What is the pH and pOH of each of the solutions given above? Recall: pH = -log [H+], pOH = -log [OH-]

Acid-Base Equilibria
Relative strengths of acids and bases
A strong acid completely transfers its protons while its conjugate base has negligible tendency to be protonated. A weak acid only partially dissociates and its conjugate base is a weak base. A substance with negligible acidity (e.g. CH4) has a conjugate base that is very strong.

Acid-Base Equilibria
Strong acids and strong bases
HCl(aq) H+(aq) + Cl-(aq) Kc = [H+][Cl-] [HCl] Since HCl is a strong acid and dissociates almost completely in the solution, [HCl] is almost zero. Therefore, HCl(aq) H+(aq) + Cl-(aq) Kc = [H+][Cl-] [HCl] [H+] = [Cl-] = initial concentration of HCl before dissociation took place The above trend goes for strong bases.

(a) Calculate the pH of 0.10 M HNO3 (b) Calculate the pH of 1.0 x 10-10 M HCl (c) Calculate the pH of 0.0011 M Ca(OH)2

Acid-Base Equilibria
Weak acids
Consider the ionization of a weak acid in water:

Ka is the acid dissociation constant at a specific temperature. Just like in molecular equilibrium, an ICE table is used in solving acid-base equilibrium problems.

Acid-Base Equilibria
Weak acids

The following approximation can be used since Ka is very small:

Acid-Base Equilibria
Weak acids

When can we do the approximation? The approximation is valid if the result is 5% of the initial concentration.

The pH of a 0.10 M solution of formic acid (HCOOH) is 2.39. What is the Ka of the acid? (1.8 x 10-4)

Acid-Base Equilibria
Percent ionization
Another measure of acid strength is percent ionization which has the formula:

The extent of dissociation of a weak acid depends on the initial concentration of the acid.

Acid-Base Equilibria
Weak bases and Base dissociation constant

What is the pH of a 0.26 M methylamine solution (Kb = 4.4 x 10-4)? What is the value of Ka for the conjugate acid of methylamine?
Acid-base properties of Salts
A salt is one of the products of an acid-base reaction (aside from water). The cation of a salt is from a base and its anion is from an acid. Salt hydrolysis refers to the reaction of a cation or an anion of a salt, or both, with water. Salts can be neutral, acidic, or basic depending on the strength of the acid and base that reacted to form the salt.

The conjugate base has a Kb value at a specific temperature. What is the value of Kb for acetate anion?

Acid-Base Equilibria
Acid-base properties of Salts If a strong acid and a strong base react, the resulting salt is neutral. If a strong acid and a weak base react, the resulting salt is acidic. If a weak acid and a strong base react, the resulting salt is basic. If a weak acid and a weak base react, the pH of the resulting solution depends on the Kb of the conjugate base and Ka of the conjugate acid.

Acid-Base Equilibria
Acid-base properties of Salts Tell whether the following salts are neutral, acidic or basic: (a) LiClO4 (b) Na3PO4 (c) NH4CN Calculate the pH of a 0.24 M sodium formate solution (HCOONa). Ka for HCOOH = 1.7 x 10-4 Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 = 1.8 x 10-5.

Buffers
A buffer solution is a solution consisting of (1) a weak acid or base and (2) its salt; both must be present. A buffer solution has the ability to resist changes in pH upon addition of small amounts of either acid or base. An example of a buffer solution is made up acetic acid (CH3COOH) and acetate anion (CH3COO-). If an acid is added to the system, the acetate ion will serve as a base to neutralize the added acid: If a base is added to the system, the acetic acid will serve as the acid to neutralize the added acid:

Which of the following are buffer systems? (a) KF/HF; (b) KBr/HBr; (c) Na2CO3/NaHCO3