THE CONCEPT OF EQUILIBRIUM

At chemical equilibrium, the forward rate of the reaction, that produces product(s), and the backwards rate of reaction, that produces reactant(s) are equal One condition for reaching equilibrium is that there is no process by which the reactant(s) or product(s) are removed from the system At equilibrium the rate at which products are formed from reactants equals the rate at which products break down to form reactants Consider the unimolecular elementary reaction process:

AB

Since this reaction as written has been defined as an elementary process, we now know something about the rate of the (forward) reaction: Reaction rate = k [A] What about the reverse reaction? The reverse reaction is also a unimolecular elementary process and, therefore, the reaction rate is equal to some rate constant times the concentration of B. o The forward rate constant (kf) will therefore be different from the reverse reaction rate constant (kr) Forward reaction rate = kf [A] Reverse reaction rate = kr [B]

Consider how this reaction would look at the molecular level if we started with pure A: At the beginning there is no B, therefore, the reverse reaction rate is 0 (since [B] = 0). At the beginning there is a lot of A, so the forward reaction rate is high (since [A] = large) As time goes by (as it always does) the concentration of A decreases (as it is used up). Therefore the forward reaction rate slows down. Also, the concentration of B starts to build up. Therefore, the reverse reaction rate starts to increase. At some point, the forward and reverse reaction rates will balance out and equal each other. Note that this does not necessarily mean the concentrations of A and B equal each other. For the rates to be equal, the productof (kf * [A]) must equal( kr *[B]). Therefore, the concentrations of A and B will be equal at equilibrium only if kf = kr. Forward Rate = Reverse Rate kf [A] = kr [B]

What this means is that at equilibrium the ratio of the concentration of B to A will always have the same value Once equilibrium is established, the concentrations of A and B do not changeThis does not mean that all reactions have stopped. Rather it means that the rates of the forward and backward reactions are equal to each other, and therefore, there is no net change in the concentration of reactant and product This is known as a dynamic equilibrium. The forward and reverse reactions are represented by a double arrow in the chemical equation: At dynamic equilibrium: The concentrations of A and B are constant The forward and reverse reaction rates are equal

THE EQUILIBRIUM CONSTANT

The Haber Process Human agriculture requires a whole bunch of ammonia-based fertilizer. Natural deposits of nitrate compounds, and bird and bat guano (i.e. poop) have been rich sources of nitrogen from which to produce ammonia based fertilizer (and also, nitrogen based explosives). Although the atmosphere is about 70% nitrogen, it was not until the early 1900's that a chemical method was developed to allow the chemical production of ammonia from nitrogen gas. This method was developed by Fritz Haber in Germany in 1912, a method known as the Haber Process:

In the Haber Process, N2 and H2 are placed together in a high-pressure tank (at several hundred atmospheres pressure), and at a temperature of several hundred C (and in the presence of a catalyst also). Under these conditions the two gases react to produce ammonia: N2(g) + 3H2(g) 2NH3(g) Extreme conditions are required because we have to break the N-N bond in N2 and this bond is a (strong) triple bond

When the N2(g) and H2(g) are combined in the Haber process, the reaction proceeds and ammonia, NH3(g) is produced The reaction seems to stop at a certain point, and some N2(g) and H2(g) remain in the sample (along with the ammonia that is produced)

Another way of saying the reaction appears to stop, is to say that at some point in time the concentrations of H2, N2 and NH3 reach a steady state (i.e. they don't appear to change) Curiously enough, the same equilibrium concentrations of H2, N2 and NH3 were observed even when the reaction was started with the vat containing only pure NH3 (i.e. pure product!)

The same equilibrium condition for the concentrations of reactants and products was reached from either direction (i.e. starting from either pure reactants, or pure product)

For a simple AB unimolecular reaction Forward Rate = Reverse Rate kf [A] = kr [B] This equation can be rearranged to relate the concentration of A to B at equilibrium:

A similar equation relates the concentrations of H2, N2 and NH3 at equilibrium in the Haber reaction

THE LAW OF MASS ACTION

In 1864 Guldberg and Waage postulated the Law of Mass Action which expresses the rela-

tionship between the concentrations of reactants and products at equilibrium in any reaction Given the following general equilibrium equation:
According to the Law of Mass Action, the equilibrium condition is expressed by the equation:

Where the brackets indicate molar concentration of the reactants and products at dynamic

equilibrium. o This expression is called the equilibrium expression for the reaction o Kc is called the equilibrium constant. Its value is what we get when we put in the observed concentrations of the reactants and products, at equilibrium, into the equilibrium expression. o The numerator (the stuff on top) of the equilibrium expression is the product of all concentrations ofproducts raised to their coefficients in the balanced equation. The denominator (the stuff on the bottom) of the equilibrium expression is the product of all concentrations of reactants raised to their coefficients in the balanced equation.

Back to Fritz Haber and his famous process to make ammonia from N2 and H2: From the Law of Mass Action, the equilibrium expression would be based upon the balanced equation: N2(g) + 3H2(g) -> 2NH3(g)

Note that once we have a balanced equation, although we may not know the reaction mechanism (i.e. underlying elementary steps or reaction intermediates), we can determine the equilibrium expression. Thus, the equilibrium expression depends only upon the balanced equation and is independent of the reaction mechanism Expressing Equilibrium Constants in Terms of Pressure, Kp Kc indicates that the equilibrium constant is in terms of concentration (in molar units) When reactants and products in a reaction are all gases we can use partial pressures in the equilibrium equation

The Magnitude of Equilibrium Constants Given the following general equation for a reaction, and the associated equilibrium expression

What can we conclude about an equilibrium constant that is LARGE? The value of the numerator (the stuff on top) must be larger than the value of the denominator (stuff on bottom) This will happen if the equilibrium concentrations of the products are larger than the reactants Thus, for a reaction with a large equilibrium constant, the equilibrium "lies to the right", meaning that the equilibrium mixture comprises mostly product What can we conclude about an equilibrium constant that is SMALL? The value of the numerator (the stuff on top) must be smaller than the value of the denominator (stuff on the bottom) This will happen if the equilibrium concentrations of the reactants are larger than the products Thus, for a reaction with a small equilibrium constant, the equilibrium "lies to the left", meaning that the equilibrium mixture comprises mostly reactants To summarize the interpretation for the magnitude of the equilibrium constant: K >> 1 Products favored K << 1 Reactants favored The Direction of the Chemical Equation and K By definition, equilibrium implies that we have both a "forward" and a "backward" reaction in a balanced chemical equation. "Forward" and "backward" are thus relative terms Consider the following reaction:

Experimentally, the value of Kc for this expression equals 0.212 (@100C) We could, however, just as equally valid, consider the reaction to be the following:

The equilibrium expression in this case would be:

The value of Kc in this case would be (1/0.212) = 4.72

The equilibrium expression for a reaction written in one direction is the reciprocal of the one for the reaction written in the reverse direction Therefore, an equilibrium constant, in the absence of information about the direction of the reaction, is ambiguous (i.e. meaningless)

HETEROGENEOUS EQUILIBRIA
Homogeneous reactions have all reactants and products existing in the same phase. A homogeneous reaction at equilibrium is termed a homeogeneous equilibrium Heterogeneous reactions will have at least one reactant or product in a different phase from the other components A heterogeneous reaction at equilibrium is termed a heterogeneous equilibrium Calcium carbonate, CaCO3 (a solid) can decompose to produce calcium oxide, CaO (another solid) and carbon dioxide, CO2 (a gas)

The system involves a gas and two solids in equilibrium:

How do we calculate the concentration (i.e. moles/volume) of a solid? The concentration of any pure liquid or solid is equal to its density (mass per unit volume) divided by its molar mass (mass per mole)

The density of a liquid or solid changes little with temperature, and is essentially a constant. o The molar mass is a characteristic of the compound in question (i.e. is a constant). o Therefore, the value of (density/molar mass), i.e. the concentration of a solid or liquid, is a constant, regardless of the amount of the solid or liquid present. With this information, the equilibrium constant for the decomposition of calcium carbonate reduces to:
o

Thus, we ignore the concentrations of solids and liquids in a heterogeneous equilibrium expression (even though these compounds must be there for the equilibrium to be established) The concentrations of gases (and solutes in solution) are included in the equilibrium expression because their concentrations can change What does the heterogeneous equilibrium expression for the decomposition of calcium carbonate (given above) tell us? At a given temperature, an equilibrium mixture of calcium oxide, carbon dioxide and calcium carbonate will always result in the same concentration of CO2(g). Since CO2 is a gas, this means that the pressure of CO2 at equilibrium will be the same value (at a given temperature) Since CaO and CaCO3 are solids, the pressure of CO2 at equilibrium is independent of the amounts of these compounds (but if one or both are missing, we won't have equilibrium, and the pressure of CO2 won't be the expected equilibrium value)

CALCULATING EQUILIBRIUM CONSTANTS

The Haber process revisited:

Haber and his coworkers were concerned with figuring out what the value of the equilibrium constant, Kc, was at different temperatures. If a temperature for the reaction was chosen such that the value of Kc was small, then it would mean that thereverse reaction is favored (equilibrium lies to the left) and very little ammonia would be produced when the reaction reaches equilibrium. This is not good, because the goal is to make ammonia. Haber did experiments where he started with various mixtures of N2, H2 and NH3 and allowed them to come to equilibrium at various temperatures He would measure the equilibrium concentrations of the various gases and determine Kc at a variety of temperatures In one experiment a mixture of H2, N2 and NH3 was allowed to reach equilibrium conditions at 472C. The concentration of gases at equilibrium was analyzed and found to contain 0.1207M H2, 0.0402M N2 and 0.00272M NH3. What value did Haber come up with for the equilibrium constant, Kc?

Kc = (0.00272)2/(0.0402)(0.1207)3 Kc = 0.105 (equilibrium lies to the left, not much ammonia will be present at equilibrium conditions) Often we do not know (or are not easily able to determine) the concentration of all products and reactants at equilibrium However, if we know the concentration of reactants and products at the start of the experiment, and the concentration of at least one product or reactant at equilibrium, and we know the stoichiometry of the balanced chemical equation, we can determine the values of the other reactants and products The steps in this method are as follows: 1. List the known initial and equilibrium concentrations of all reactants and products involved in the equilibrium 2. For those reactants or products, for which both the initial and equilibrium concentrations are known, calculate the change in concentration that occurs as the system reaches equilibrium 3. Use the stoichiometry of the reaction to calculate the predicted changes in concentration for all the other reactants and products in the equilibrium 4. From the initial concentrations, and the changes in concentration, calculate the equilibrium concentrations (and Kc)

In one of Haber's experiments, 0.025 mol of H2(g) and 0.010 mol of N2(g) are combined in a 2L vessel at 472C. The mixture is allowed to come to equilibrium and the concentration of NH3(g) is observed to be 3.18 x 10-5M. Calculate Kcfor the Haber reaction at this temperature.

1. The known initial and equilibrium concentrations for the different compounds are: Initial concentrations: H2(g) is 0.025 mol / 2L = 0.0125M N2(g) is 0.010 mol / 2L = 0.005M NH3(g) is 0M initially Final (equilibrium) concentrations: H2(g) ? N2(g) ? NH3(g) is 3.18 x 10-5M 2. Initial and final concentrations are known only for NH3(g): [NH3(g)] = Equilibrium concentration - Initial concentration [NH3(g)] = 3.18 x 10-5M - 0M = 3.18 x 10-5M = the amount of ammonia produced in the reaction 3. Stoichiometry of balanced equation: N2(g) + 3H2(g) 2NH3(g), therefore, stoichiometry is: [N2] 3[H2] 2[NH3] Thus, if 3.18 x 10-5M of NH3 is being produced, (3.18 x 10-5M NH3) * (1 N2 / 2 NH3) = 1.59 x 10-5M of N2 must have been consumed and (3.18 x 10-5M NH3) * (3 H2 / 2 NH3) = 4.77 x 10-5M of H2 must have been consumed 4. Calculation of concentration of all reactants and products at equilibrium by knowing initial concentrations and how much was consumed: N2 started with 0.005M, and 1.59 x 10-5M of N2 was consumed, therefore, at equilibrium there was (0.005M - 1.59 x 10-5M) = 4.98 x 10-3M of N2 H2 started with 0.0125M, and 4.77 x 10-5M of H2 was consumed, therefore, at equilibrium there was (0.0125M - 4.77 x 10-5M) = 1.245 x 10-2M of H2 NH3 concentration at equilibrium was given as 3.18 x 10-5M Kc = [NH3]2/[N2][H2]3 = (3.18 x 10-5)2 / (4.98 x 10-3)(1.245 x 10-2)3 = (1.01 x 10-9) / (4.98 x 10-3)(1.95 x 10-6) = 0.104 Relating Kc and Kp For a gas we can express the equilibrium constant in terms of concentration (molarity) or in units of pressure. How are these related?

Molarity relates the number of moles per unit volume (n/V) The ideal gas law, PV = nRT, includes terms for both number of moles and volume PV = nRT P = (n/V)RT P = MRT For a gaseous substance, A, the partial pressure of A is equal to the molarity times the gas constant R and temperature T in Kelvin PA = [A](RT)

Note: P = MRT can be manipulated to solve for R, the gas constant: R =P/MT. This provides an interpretation for the meaning of the gas constant - it is a way to relate the molarity of a gas sample to its pressure and temperature Thus, Kc and Kp are related, and in fact Kp = Kc(RT) n The value n is the change in the number of moles of gas upon going from reactants to products. It is equal to the (number of moles of gaseous products - number of moles of gaseous reactants) N2O4(g) 2NO2(g) Dn = (2-1) = 1 Kp = Kc(RT)1 = Kc(RT)

APPLICATIONS OF EQUILIBRIUM CONSTANTS

This section of our study of equilibrium constants deals with various types of calculations, including: 1. How to figure out in which direction a reaction will go (i.e. towards making product, or more reactant) 2. Calculating equilibrium concentrations. This may involve knowing equilibrium values for some of the reactants and products and determining the concentration of an unknown. 3. Alternatively, we may be provided with the starting concentrations of reactants and products and may be asked to find the equilibrium concentrations The Magnitude of K The magnitude of the equilibrium constant, K, indicates the extent to which a reaction will proceed: If K is a large number, it means that the equilibrium concentration of the products is large. In this case, the reaction as written will proceed to the right (resulting in an increase in the concentration of products) If K is a small number, it means that the equilibrium concentration of the reactants is large. In this case, the reaction as written will proceed to the left (resulting in an increase in the concentration of reactants) Knowing the value of the equilibrium constant, K, will allow us to determine: The direction a reaction will proceed to achieve equilibrium The ratios of the concentrations of reactants and products when equilibrium is reached Predicting the Direction of a Reaction The value of Kc for the Haber reaction at 472C is 0.105. If we place the following amounts of H2(g), N2(g) and NH3(g) in a 3.0L container at 472C will the N2(g) and H2(g) react to form more NH3(g)? N2(g) + 2H2(g) 2NH3(g) H2(g) = 0.5 mol N2(g) = 8.3 mol NH3(g) = 1.8 mol The amounts of the components is converted into concentrations (mol/L or M)and the mol value is divided by the volume of the container (gases expand to fill their container) Concentration of H2(g) = 0.5mol/3.0L = 0.167M Concentration of N2(g) = 8.3mol/3.0L = 2.77M Concentration of NH3(g) = 1.8mol/3.0L = 0.600M

We need to state the equilibrium expression for this reaction, based upon the balanced equation: N2(g) + 3H2(g) <=> 2NH3(g)

Inserting the initial values of reactants and products into the equilibrium expression we get the following: = (0.600)2/((2.77)*(0.167)3) = 27.9 How does this number compare to the value of the equilibrium constant at this temperature? The "initial value of the equilibrium constant" is 27.9, at equilibrium we know that this must decrease to 0.105 For the value of Kc to decrease to the experimentally expected value at equilibrium, the concentration of NH3(g) must decrease, and/or the concentrations of N2(g) and H2(g) must increase o Therefore, the reaction would have to proceed to the left (increasing reactants and decreasing product concentrations) When we substituted the initial values for the concentrations of the reactants and products into the equilibrium expression the number we came up with is called the Reaction Quotient (Q) (i.e. "the initial value of the equilibrium constant") If Q = Kc, then the system is already at equilibrium If Q > Kc, then essentially we have too much product and the reaction will proceed to the left (to reduce the concentration of product and increase the concentration of product) If Q < Kc, then essentially we have too little product and the reaction will proceed to the right (to produce more product and decrease the concentration of reactant) Calculation of the Equilibrium Concentration of a Reactant or Product Many types of equilibrium problems deal with determining how much of a product (or reactant) we will have once a reaction reaches equilibrium. The following example involves Kp and partial pressures for our friend, the Haber reaction: At 500 Kp = 1.45 x 10-5 for the Haber reaction: N2(g) + 3H2(g) <=> 2NH3(g) In a sample of N2(g), H2(g) and NH3(g) at equilibrium in a Haber reaction the partial pressure of the H2(g) is 1.32 atm, and the partial pressure of the N2(g) is 0.648 atm. What is the partial pressure of the NH3(g) in the equilibrium mixture? In this problem we have a homogeneous equilibrium of gases and the equilibrium constant, Kp, is given in terms of partial pressures of the component gases. For this reaction, the definition of Kp is given as

The equilibrium partial pressures of H2(g) and N2(g) are given, as is the value for Kp 1.45 x 10-5 = (PNH3)2 / ((0.648)*(1.32)3) We can solve for the partial pressure of NH3(g) PNH3 = (2.16 x 10-5)1/2 PNH3 = 4.64 x 10-3 atm If there is any doubt that we have done the calculations correctly, we can substitute this value (along with the equilibrium partial pressures for H2(g) and N2(g)) into the equilibrium expression and make sure that we get the correct value for Kp

Solving equilibrium concentrations of all components in a reaction Sometimes an equilibrium problem will provide the value for the equilibrium constant and the initial concentration of all species. The question is then to calculate the concentration of all species at equilibrium. This is a more difficult type of problem. The following example is one for the reaction between nitrogen and oxygen. Nitrogen and oxygen can react in the following equation: N2(g) + O2(g) 2NO(g) Kc = 2.1 x 10-3 (2500K) A reaction is setup with 5.75M N2(g), 4.89M O2(g) and 0M NO(g). What will be the equilibrium concentrations of all components? XM = conc of N2(g) that reacts as reaction goes to equilibrium. Therefore: Equilibrium conc of N2(g) = (5.75M - XM) From the stoichiometry of the balanced equation, if XM of N2(g) reacts, then an equivalent concentration of O2(g) must react. Therefore: Equilibrium conc of O2(g) = (4.89M - XM) Furthermore, from the stoichiometry of the balanced equation, XM of N2(g) reacting will result in 2XM of NO(g) being produced. Therefore: Equilibrium concentration of NO(g) = 2XM Setting up the equilibrium constant equation: 2.1 x 10-3 = [NO]2 / ([N2][O2]) = (2X)2 / {(5.75 - X)(4.89 - X)} 2.1 x 10-3 = 4X2 / (28.1 - 10.6X + X2) (2.1 x 10-3)*(28.1 - 10.6X + X2) = 4X2 0.0590 - 0.0223X + 0.0021X2 = 4X2 4.00X2 + 0.0223X - 0.059 = 0 Even for simple reaction we are often faced with a quadratic solution for x: 2 For equations of the form ax + bx + c = 0, the solution(s) for x are given by the quadratic equation:

We may have more than one possible solution for x, but only one will make sense

Quadratic solutions: X = 0.119 or -0.124 (can't have a negative value). Therefore, the equilibrium concentrations are: N2(g) = (5.75 - 0.119) = 5.63M O2(g) = (4.89 - 0.119) = 4.77M NO(g) = (2 * 0.119) = 0.238M Note: plugging these values back into the equilibrium constant expression will allow us to check our answer: Kc = [NO]2 / ([N2][O2]) = (0.238)2 / (5.63)(4.77) Kc = 2.11 x 10-3 (this is pretty close considering round off errors) The value of Kc for the Haber reaction at 472C is 0.105. A 2.0L flask is filled with 0.2 mol of H2(g), 1.8 mol of N2(g) and 0.5 mol of NH3(g). What are the concentrations of H2(g), N2(g) and NH3(g) at equilibrium? The equilibrium constant Kc defines the amount of reactant and product in terms of concentration (moles/L). So the first thing to do is convert all amounts into molar concentrations: N2(g): 1.8mol/2.0L = 0.9M H2(g): 0.2mol/2.0L = 0.1M NH3(g): 0.5mol/2.0L = 0.25M

Next, calculate the reaction quotient, Q, to figure out whether the reaction will go to the right or left to attain equilibrium: Q = (0.25)2 / ((0.9)*(0.1)3) Q = 69.4 Q = 69.4 is a lot larger than the value of Kc = 0.105. Therefore, we are starting out with too much product and the reaction will proceed to the left, to produce more reactant. When the reaction does goes to the left, as predicted by the reaction quotient, the breakdown of NH3(g) product to produce N2(g) and H2(g) reactants will follow the stoichiometry of the balanced equation:

N2(g) + 3H2(g) 2NH3(g)

Thus, for every mole of NH3(g) that decomposes, 0.5 mole of N2(g) will be produced and 1.5 mole of H2(g) will be produced We know that a certain amount of NH3(g) will have to break down in order for the reaction to achieve equilibrium. We can set this unknown amount to a variable, x Thus, the concentrations of H2(g), N2(g) and NH3(g) at equilibrium will equal the following: Equilibrium concentration of NH3(g) = (starting concentration - amount that decomposes) = 0.25M - x Equilibrium concentration of H2(g) = (starting concentration + (1.5 * amount of NH3(g) that decomposes)) = 0.1M + 1.5x Equilibrium concentration of N2(g) = (starting concentration + (0.5 * amount of NH3(g) that decomposes)) = 0.9M + 0.5x The above amounts describe the equilibrium concentrations of the reactants and products and can therefore be inserted into the description of the equilibrium expression, and are set equal to the value for Kc:

0.105 = (0.25 - x)2 / ((0.9 + 0.5x)*(0.1 + 1.5x)3) Although there is only one variable, this is a fairly complicated expression. It turns out that there are several possible mathematical solutions for x in this equation:

The first solution (a negative value for x) does not make any sense because product must be degraded not increased. So we can exclude this solution The starting concentration of NH3(g) is 0.25M. The equilibrium concentration is (0.25M x). The equilibrium concentration cannot be less than 0. Therefore, any solution greater than 0.25 is meaningless (i.e. incorrect) This leaves only one possible solution, x = 0.178M. Thus the equilibrium concentrations of the various components in the reaction are: o Equilibrium concentration of NH3(g) = (0.25M - 0.178) = 0.072M o Equilibrium concentration of H2(g) = (0.1M + 1.5*0.178) = 0.367M o Equilibrium concentration of N2(g) = (0.9M + 0.5*0.178) = 0.989M Finally, we can check our answer by plugging these values into the equation for the equilibrium constant and making sure we get the right answer (i.e. 0.105 in this case)

LE CHTELIER'S PRINCIPLE
In order to try to figure out how to optimize the production of ammonia from hydrogen and nitrogen, Haber studied the equilibrium concentrations of ammonia in his famous process:

N2(g) + 3H2(g) 2NH3(g) He noted the equilibrium concentration of ammonia at different temperatures (while keeping pressure constant) He also noted the equilibrium concentration of ammonia at different pressures (while keeping the temperature constant) Haber observed that the equilibrium concentration of ammonia: o decreased with increasing temperature, o and increased with increasing pressure The underlying basis behind both of these phenomena was described by Henri-Louis Le Chtelier; Le Chtelier's principle: If a system is in equilibrium, and this equilibrium is perturbed by a change in temperature, pressure or theconcentration of a reactant or product, then the system will shift its equilibrium so as to counteract the effect of this perturbation

A Change in Reactant or Product Concentration At equilibrium the rate of the forward reaction is equal to the rate of the reverse reaction. Le Chtelier's principle states that if the concentration of one of the components of the reaction (either product or reactant) is changed, the system will respond in such a way as to counteract the effect If a substance (either reactant or product) is removed from a system, the equilibrium will shift so as to produce more of that component (and once again achieve equilibrium) If a substance (either reactant or product) is added to a system, the equilibrium will shift so as to consume more of that component (and once again achieve equilibrium) As an example, consider the Haber reaction: N2(g) + 3H2(g) 2NH3(g) What would happen if we started with a Haber reaction at equilibrium, and then suddenly added some H2(g) to the reaction mix? The following is a graphical representation of how the concentrations of the individual components, and the overall system, would react in response to adding H2(g): What has happened to the equilibrium of the system in response to the added H2(g)? Prior to the addition of H2(g) the system is in equilibrium. This can be seen because the concentrations of the different components do not change with time (the forward and reverse rates must be equal)

When the H2(g) is added, we see that the system responds by consuming N2(g) and producing NH3(g). Forward rate = k1 [N2] [H2]3 The production of NH3(g) requires both N2(g) and H2(g) as reactants. Therefore, the production of NH3(g) not only consumes N2(g) but also H2(g)

The addition of H2(g) causes the balance of the system to shift in favor of the forward reaction (i.e. the production of NH3(g) from N2(g) and H2(g). Thus, some of the added H2(g) is consumed, and thus, the system responds to counteract the perturbation caused by the added H2(g) N2 + 3H2 2NH3 (reaction is driven "to the right" by the effects of added H2) After some time, the system reaches a new state of equilibrium. It will not be identical to the original state, however. Although the system has responded to resist the effects of the added H2(g), the new equilibrium state contains a slightly higher concentration of NH3(g), and slightly lower concentration of N2(g) (as well as a slightly higher concentration of H2(g). The overall ratio of [NH3]2/([N2]*[H2]3) is the same as before at equilibrium (i.e. the value of Kc does not change) What would happen if we repeated the experiment, but added NH3(g) instead of H2(g)? The system would respond by decomposing some of the added NH3(g) and a new equilibrium condition would be established (with slightly higher concentrations of H2(g) and N2(g) - as well as slightly higher equilibrium concentrations of NH3(g). Reverse rate = k-1 [NH3]2

At the new equilibrium the concentrations of reactants and product is slightly different from before, but Kc has the same value

Effects of Volume and Pressure changes A chemical system in equilibrium can respond to the effects of pressure also. According to Le Chtelier's Rule, if the pressure is increased on a system, it will respond by trying to reduce the pressure. How does it do this? We are primarily concerned with homogeneous gaseous reactions The stoichiometry of the reaction may lead to a greater number of molecules on one side of the equation. For example, in the Haber reaction, N2(g) + 3H2(g) 2NH3(g) there are twice as many moles of reactants as products If the Haber reaction were in equilibrium, and the pressure was increased, the reaction would respond to oppose the increase in pressure. It could accomplish this by shifting the equilibrium to the right (producing NH3(g)) o This would reduce the overall number of moles in the reaction, and therefore, lower the pressure An interesting point about pressure effects is that they do not cause a change in the value of the equilibrium constant, K(as long as T is held constant). Their affects are upon concentration of reactants and products For the Haber process at 472C, the value of K is 0.105. An example of one such system in equilibrium at this temp might include [H2]=0.121M, [N2]=0.0402M and [NH3]=0.00272M

K for the Haber process is defined as [NH3]2/([N2]*[H2]3)

If the volume of the sample is suddenly decreased by half, from the ideal gas equation the concentrations of the components in the sample have doubled (and the pressure has doubled): PV = nRT P = (n/V)RT The concentration of the components in this reaction at this new pressure would therefore be [H2]=0.242M, [N2]=0.0804M and [NH3]=0.00544M The reaction quotient, Q, at this new condition would therefore be: (0.00544)2/(0.0804*0.2423) = 0.0262. This is less than K=0.105, thus, in response, the reaction equilibrium shifts to the right, consuming reactants and producing NH3(g) product. This shift to the right reduces the number of molecules, therefore, the pressure is reduced.

Effect of Temperature Changes The intrinsic value of K does not change when we increase concentrations or pressures of components in a reaction. However, almost every equilibrium constant (K) changes in response to changes in temperature. Once again, we can apply Le Chtelier's rule in order to predict the effects of temperature changes upon chemical reactions Most chemical reactions have some heat change associated with the reaction. (Note, the energy of a reaction can be used to either do work - i.e. accelerate an object against some force - or to change temperature. We will consider reaction conditions under which no work is done, and therefore all energy changes associated with reactions will be manifested by temperature changes) Exothermic reactions are associated with heat release when the reaction proceeds in the forward direction Endothermic reactions are associated with heat release when the reaction proceeds in the reverse direction (i.e.heat is absorbed in the forward direction) These two types of reactions and their associated heat changes can be written as: Exothermic: Reactants Products + Heat

Endothermic: Reactants + Heat Products If temperature is increased, the equilibrium will shift so as to minimize the effect of the added heat

The reaction will shift in the appropriate direction such that the added heat is absorbed

When heat is added to exothermic reactions at equilibrium, products will be consumed to produce reactants (shift to the LEFT) When heat is added to endothermic reactions at equilibrium, reactants will be consumed to produce products (shift to the RIGHT)

Based on this behavior, what is the effect of T upon K? Assume K = 1.0 for an exothermic reaction at equilibrium. Added heat causes the reaction to shift to the left. Reactants <= Products + Heat Thus, 1.0 must represent a reaction quotient, Q, that is too large in comparison to the new value of K. Thus, the effect of increasing temperature on an exothermic reaction is to lower the value of K. Conversely, the effect of increasing temperature on an endothermic reaction is to increase the value of K

The Effect of Catalysts A catalyst lowers the activation energy barrier, Ea Although the activation energy barrier is a different magnitude for the forward and reverse reactions, the change in the activation energy ( Ea) is the same for both the forward and reverse reactions Therefore, a catalyst changes the rate at which equilibrium is achieved, but does not change the composition of the equilibrium mixture (i.e. does not alter the equilibrium constant, K)

Acid-Base Equilibria
BRNSTEAD-LOWRY ACIDS AND BASES The Arrhenius definition of an acid and a base: + Acids - substances that when dissolved in water release H ions Bases - substances that when dissolved in water release OH ions + The definition of an Arrhenius acid and base emphasizes the H and OH ions in water Proton Transfer Reactions HCl is an Arrhenius acid: When HCl dissolves in water it actually transfers a proton to a water molecule: HCl(g) + H2O(l) H3O+(aq) + Cl-(aq) + + The recognition that the release of H ions by acids involves H transfer led to a new proposal for the definition of what is an acid, and what is a base The Brnstead-Lowry definition of an acid and a base: Acids - a substance that can transfer a proton to another substance Base - a substance that can accept a proton from another substance These definitions emphasize proton transfer, and can include solvents other than water (aqueous solutions are not part of the definition, proton transfer is the key feature) The definition was developed independently in 1923 by Johannes Brnstead and Thomas Lowry HCl(g) + H2O(l) H3O+(aq) + Cl-(aq) In the reaction of HCl with H2O, HCl is a Brnstead-Lowry acid (donates a proton to H2O), and the H2O (in this particular reaction) is a Brnstead-Lowry base (accepts a proton from the HCl) HCl(g) + NH3(g) Cl-(g) + NH4+(g) In the reaction of HCl with NH3, a proton is transferred from the HCl to the NH3. o The HCl is the Brnstead-Lowry acid o NH3 is the Brnstead-Lowry base o H2O is not involved in the reaction (or definition) of the acid or base in this reaction NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) In the above reaction of ammonia with water, the ammonia is a Brnstead-Lowry base, and the H2O is acting as a Brnstead-Lowry acid A molecule that can act as both a Brnstead-Lowry acid or a Brnstead-Lowry base (depending on the reaction in question) is termed amphoteric

The ammonia is also an Arrhenius base (it increases the concentration of OH- ions in water) An acid and a base always work together to transfer a proton A substance can only work as a Brnstead-Lowry acid (i.e. donates a proton), if another substancesimultaneously acts as a Brnstead-Lowry base (i.e. accepts the proton) o To be a Brnstead-Lowry acid, a molecule must have a H atom that can it can lose as an H+ ion o To be a Brnstead-Lowry base, a molecule must have a non-bonding pair of electrons that it can use to bind the H+ atom (this non-bonding pair will form the basis of the "shared" electrons in the new covalent bond with the H atom)

Conjugate Acid-Base Pairs In any acid-base equilibrium both the forward and reverse reactions involve proton transfer reactions. For example, the general reaction of a Brnstead-Lowry acid with water proceeds as follows: HA(aq) + H2O(l) A-(aq) + H3O+(aq) acid + base base + acid In the forward reaction, HA donates a proton to H2O o HA is the Brnstead-Lowry acid o H2O is the Brnstead-Lowry base + In the reverse reaction, H3O donates a proton to A + o H3O is the Brnstead-Lowry acid o A is the Brnstead-Lowry base When HA behaves as an acid and donates a proton, what remains is A-, which behaves like a base + When H3O behaves as an acid and donates a proton, what remains is H2O, which (in this reaction) behaves like a base (although H2O is amphoteric) HA and A are termed a conjugate acid-base pair. They differ only in the presence or absence of a proton. o A is the conjugate base of HA + H3O and H2O are also a conjugate acid-base pair. + o H3O is the conjugate acid of H2O In any acid-base proton transfer reaction there will be conjugate acid-base pairs

Relative Strengths of Acids and Bases A strong acid is a molecule that has a strong preference to donate a proton. Thus, its conjugate base will have a weak tendency to accept a proton

A strong base is a molecule that has a strong preference to accept a proton Thus, its conjugate acid will have a weak tendency to donate a proton There is an inverse relationship between the strength of an acid and its conjugate base (likewise a strong base and its conjugate acid) All molecules of a strong acid in water will donate their protons (to H2O) The conjugate base has no tendency to be protonated. Weak acids have conjugate bases that have a moderate tendency to be protonated. Thus, in solution, only a fraction of the molecules of a weak acid will donate a proton. There will be a significant concentration of both the acid and conjugate base forms in solution What about molecules that contain H atoms, e.g. methane (CH4), but do not appear to have any acidic character? Their conjugate bases must be quite strong! o CH3 is the conjugate base if CH4 behaves as an acid + o CH3 is such a strong base that it strips H from H2O with such vigor that NO CH3- will remain in solution o Thus, CH4 (the conjugate acid to CH3 ) is technically an incredibly weak acid absolutely NO molecules will donate a proton If we were to consider the "reaction" of methane with water we would have: CH4(g) + H2O(l) CH3-(aq) + H3O+(aq)

acid + base base + acid The reaction proceeds entirely to the left o When comparing CH3 and H2O (both are bases in this reaction), the CH3 is the stronger base + + o When comparing CH4 and H3O , the H3O is the stronger acid CH4(g) + H2O(l) CH3-(aq) + H3O+(aq)

acid + base stronger base + stronger acid In acid-base reactions, the reaction proceeds in the direction where a proton is transferred from the stronger acid to the stronger base Strong Acids and Bases Strong acids and bases are strong electrolytes and exist in solution entirely as ions. There are relatively few common strong acids and bases Strong Acids The monoprotic (one proton) strong acids: HCl (hydrochloric acid) HBr (hydrobromic acid) HI (hydroiodic acid) HNO3 (nitric acid) HClO3 (chloric acid) HClO4 (perchloric acid) The diprotic (two protons) strong acid: H2SO4 (sulfuric acid) These acids are completely ionized in H2O(l). Thus, the reaction is represented with a single arrow in the direction of proton donation: HCl(aq) + H2O(l) Cl-(aq) + H3O+(aq)

Or an equally valid equation for an aqueous solution of HCl: HCl(aq) Cl-(aq) + H+(aq) The protons from an aqueous solution of a strong acid are typically in such vast excess to the natural ionization of water that their concentration determines the [H+] of an aqueous solution Strong Bases There are few common strong bases. They are typically the ionic hydroxides of group 1A metals, and some of the heavier group 2A metals: LiOH, NaOH, KOH, etc. Ca(OH)2, Sr(OH)2, Ba(OH)2 These molecules ionize completely in aqueous solution. The [OH ] of an aqueous solution of a strong base is determined by the concentration of the base - it is in vast excess to the natural ionization of water Strongly basic solutions can also be produced by certain substances that react with water to form OH- ions 2 Oxide ion (O ) is an example of this (in the form of metal oxides, e.g. CaO) O2-(aq) + H2O(l) 2OH-(aq) CaO(aq) + H2O(l) 2OH-(aq) + Ca2+(aq)

O2- will react completely with H2O to produce OH- ion (i.e. it is a strong base) Other strong bases like O2- include H- and N3-

Periodic table and acid/base properties of compounds Bimolecular compounds of the form X-H (i.e. group 7 hydrides) will have different acid strengths depending on the ease with which the proton can be released (i.e. the ease with which the X-H bond can be broken). The further the bonding electrons are from the nucleus, the less energy is required to ionize them completely. In this regard, as you move down the periodic table the atomic radii increases and valence electrons are further away from the nucleus. Thus, bond strengths generally decrease as you move down the periodic table, and it requires less energy to ionize a proton in an X-H compound. The easier it is to release a proton, the more acidic the compound. Thus, group 7 hydrides are stronger acids as you move down the periodic table:

Similarly, the electronegativity of the elements generally increases as you move to the right of the periodic table. For any two elements that are bonded together, it is easier to break the bond and ionize the two atoms if there is a large difference in electronegativities.

The extreme case would be a metal halide - the large electronegativity difference means that they don't share bonding electrons, rather they ionize readily (since the metal wants to give up its valence electron and the halide wants to get one). Thus, the greater the electronegativity difference between a hydrogen and the other atom in a H-X bond, the easier to ionize and thus the stronger the acid. The electronegativity of H is about the same as carbon. So, as you move right in the periodic table beyond beyond carbon, the stronger the acid for X-H bonds (i.e. CH4< NH3 < H2O < HF as far as acid strength):

Another effect upon the ability to ionize an X-H bond is the effect of an electron-withdrawing group (i.e. a group with a large electronegativity) in the proximity of an X-H bond. This is most often observed for halides bound to various locations within carboxylic acid compounds. The closer they are bonded to the carboxylic acid ionizable proton (-O-H bond) the stronger the carboxylic acid. The reason for this is that their high electronegativity tends to delocalize electrons and withdraw them towards the halide. This effect can be distributed over the molecule and influence the electrons comprising the X-H bond. If they are withdrawn away from the H, then it is easier to ionize the H (and the acid will be stronger). Here are examples:

DISSOCIATION OF WATER
Acids and Bases - Brief Review Acids have a sour or tart taste (but don't use this method to identify if a compound is an acid) Bases have a bitter taste, and have a slippery feel When bases are added to acids, they lower the amount of acid. When acids and bases are mixed together in appropriate proportions, they are completely neutralized (and their characteristic acid/base properties disappear altogether) 1830 - It was known that all acids contain hydrogen, but not all hydrogen-containing compounds were acids 1889 - Svante Arrhenius (he of the Arhhenius equation) connected acidic properties with the presence of H+ions andbasic properties with the presence of OH- ions + If a solution contained more H than OH ions, then it was acidic + If a solution contained more OH than H ions, then it was basic + H and OH ions can react with each other to form H2O molecules during neutralization reactions

The Dissociation of Water Pure water consists almost entirely of H2O molecules. While this may seem like a redundant statement, the point is that H2O is essentially a non-electrolyte. Pure water is a poor conductor of electricity because it does not ionize to any great extent. What little ionization of water does occur results in the production of H+ and OH- ions. At room temperature, one in abillion water molecules will ionize: H2O(l) H+(aq) + OH-(aq) This process is termed the auto-ionization of water The equilibrium expression for the auto-ionization reaction is:

The concentration of pure H2O is about 55M. The concentration of water is essentially

unchanged during chemical reactions involving dilute aqueous solutions (i.e. where the "solute" is in very low concentrations compared to the pure 55M water). As a result, the term for the concentration of water is considered to be a constant in the equilibrium equations involving dilute aqueous reactions. Therefore:

The constant, Kw, is called the ion-product constant. At 25C, the value of Kw is 1 x 10

-14

The presence of other ions in dilute aqueous solution does not significantly perturb this equilibrium constant. Therefore, this value is used for pure water and such solutions. Based on this equilibrium constant, if we know the concentration of either H+ or OH- ions in solution, then we can derive the concentration of the other ion [H+] = 1 x 10-14 / [OH-] [OH-] = 1 x 10-14 / [H+] A solution for which [H+] = [OH-] is said to be neutral [H+][OH-] = 1 x 10-14 if at neutrality [H+] = [OH-] then we can substitute into the above equation to yield: [H+][H+] = 1 x 10-14 [H+]2 = 1 x 10-14 [H+] = 1 x 10-7 (true for neutral solutions) o Most aqueous solutions are not neutral o As the concentration of one of these ions increases, the other must decrease according to the equilibrium constant

The Proton in Water The auto-ionization of water: H2O(l) H+(aq) + OH-(aq) An H+ ion is a hydrogen atom that has lost its (one and only) valence electron. In other words, it is a naked proton. This proton is quite reactive; it wants two valance electrons in order to form a stable noble gas valence electron configuration (like He)

The proton in solution has a high affinity for a non-bonding pair of electrons in neighboring water molecules, and will form a covalent bond to the oxygen atom in water molecules:

The H3O+(aq) ion is called a hydronium ion + + o Chemists use H and H3O terms interchangeably to represent the hydrated proton in acidic aqueous solutions + + o The H ion is most often used because its simple and convenient, but H3O is more closest the physical state of this hydrogen ion in solution o Production of the hydronium ion from the auto-ionization of water is often written not in two distinct steps, but as resulting from the interaction of two water molecules: H2O(l) H+(aq) + OH-(aq) H+(aq) + H2O(l) H3O+(aq) H2O(l) + H2O(l) H3O+(aq) + OH-(aq) Or 2H2O(l) H3O+(aq) + OH-(aq)

The equilibrium equation for this ionization would be:

This would seem to give a different constant than the above expression for the equilibrium constant arising from a single water molecule. However, since the concentration of H2O(l) is constant, the [H2O]2 term is also a constant.

Thus, the value of the equilibrium constant is the same (i.e. it depends on the product of the concentration of the OH- ion and the H+ or H3O+ ion). And [H+] is interchangeable with [H3O+]

Thus, H+ is interchangeable with H3O+

THE pH SCALE
The concentration of H+ ion in solution is a pretty small number that can, nonetheless, vary over a considerable range. + To conveniently represent the magnitude and range of concentration that the H ion can have in aqueous solutions, the term pH is used + pH is defined as the negative logarithm (base 10) of the H ion concentration pH = -log [H+] -pH = log[H+] 10 -pH = [H+]

What is the pH of a neutral solution at 25? -7 Under this condition, the concentration of hydrogen ion is 1.0 x 10 M -7 pH = -log(1.0 x 10 ) = -(-7.0) = 7.0 What is the pH of an acidic solution? + An acidic solution is one where we have an increase in [H ] + -7 + If a neutral solution has a [H ] of 1 x 10 M, then an acidic solution must have a [H ] that is greater than 1 x 10-7M + -6 For example, a solution with a [H ] = 1 x 10 M will be acidic. What will be the pH of this solution? -6 pH = -log(1.0 x 10 ) = -(-6.0) = 6.0 Because of the negative sign in the log term of the definition of pH, acidic solutions (i.e. those with increasing concentrations of H+ ions) will have increasingly lower values of pH (i.e. pH 1.0 is a potent acid and this pH is used to help digest your food in your stomach). What is the pH of a basic solution? -7 A basic solution is one in which the [OH ] is greater than 1 x 10 M -5 -7 For example, a solution has a [OH ] = 1.0 x 10 M (this is greater than 1 x 10 M, and so this solution is basic)

Basic solutions will have increasingly higher values of pH (i.e. pH 12 would be a potent base) The nature of the pH scale, based upon the -log[H+], is that a 10 x fold change in [H+] results in a single unit change in the pH value. + -7 A pH 7.0 solution has a [H ] of 1 x 10 M. If we increase the concentration 10 x fold (to 1 x 10-6M) the pHdecreases by 1 unit (to pH 6.0) + -4 A pH 4.0 solution has a [H ] of 1 x 10 M. If we decrease the concentration 10 x fold (to 1 x 10-5M) the pHincreases by 1 unit (to pH 5.0) Although the concentration of [H+] may seem very low indeed, even small changes can have a big impact on chemical reactions that include [H+] as a component in their reaction + For reactions that are first order in [H ] doubling the concentration (even though the starting concentration is a very small amount) can double the reaction rate Blood is approximately pH 7.4. If the pH of blood varies by as much as 0.5 pH units outside this value, illness and death may result Other "p" Scales By convention, the negative log of a quantity is labeled p(quantity) For example, we could reference the quantity of OH ions directly: pOH = -log [OH-] From the definition of Kw: Kw = [H+][OH-] = 1 x 10-14 -log(Kw) = (-log([H+]) - log([OH-]) = 14 -log(Kw) = pH + pOH = 14 Measuring pH pH meters; detect changes in voltage in response to changes in pH Indicator dyes; change colors at different pH's.

Bromthymol Blue - changes color from yellow (pH 6) to blue (pH 7.4) physiologically useful indicator o Phenolphthalein - changes color from colorless (pH 8) to pink (pH 9) - often used to determine the endpoint in an acid/base titration
o

WEAK ACIDS
Most acids are weak acids - they only partially ionize in aqueous solution + If weak acids only partially ionize, then the [H ] that is produced is less than the total concentration of acid addedto the solution (note: a strong acid dissociates completely and therefore the [H+] is equal to the concentration of acid added to a solution). + Since the [H ] produced by the ionization of weak acids is less than the concentration of acid added to the solution, you cannot calculate the pH directly from the concentration of acid (again, this would only be possible with strong acids that dissociate completely). The extent of their ionization can be expressed by using the equilibrium constant and equilibrium equation: HA(aq) H+(aq) + A-(aq)

Ka is the equilibrium constant for the ionization of an acid, often referred to as the acid dissociation constant What happens if the hydrated proton is represented by H3O+(aq) instead of H+(aq)? HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Here the H2O is in liquid form, and therefore, its concentration never changes (and we can consider it to be a constant in the expression

And Ka is the same expression in both cases

Weak acids are often composed entirely of C, H and O atoms H atoms are often bonded to either C or O atoms o C electronegativity = 2.5 o H electronegativity = 2.1 o O electronegativity = 3.5 The H atoms bonded to C do not ionize (not a polar bond) It is one or more H atoms bonded to an O atom that can ionize in water (due to difference in electronegativity) Weak acids are often carboxylic acids:

The magnitude of Ka is an indication of the tendency of the H atom to ionize + o If Ka is large, it means that the concentration of H ion is large, and this means the acid likes to ionize (the more it ionizes, the stronger the acid)

Thus, the larger the value of Ka, the stronger the acid Phenol is a very weak acid, its Ka = 1.3 x 10-10 Hydrofluoric acid is a weak acid, but is considered to be one of the strongest weak acids (if that makes sense, sort of like "Jumbo Shrimp"), its Ka = 6.8 x 10-4 -3 Values for Ka for weak acids is typically less than 1 x 10
o

The pH of a 0.25M solution of acetic acid (HC2H3O2) is found to be 2.68. What is Ka for this solution and what % of the acid ionized? pH = -log[H+] 2.68 = -log[H+] -2.68 = log[H+] 10-2.68 = [H+] 2.09 x 10-3M = [H+] Balanced equation and equilibrium equation: HC2H3O2(aq) H+(aq) + C2H3O2-(aq) Ka = [H+][C2H3O2-] / [HC2H3O2] -3 + -3 From the stoichiometry, 2.09 x 10 M of H ions would be produced if 2.09 x 10 M of acetic acid decomposed. -3 Likewise, 2.09 x 10 M of conjugate base (C2H3O2 ) would be produced. -3 If 2.09 x 10 M of acetic acid decomposed, then the amount of acetic acid at equilibrium would be equal to (what we started with - amount that decomposed) = (0.25M - 2.09 x 103 M) = 0.248M Ka = (2.09 x 10-3) * (2.09 x 10-3) / (0.248) Ka = 1.76 x 10-5 + The % of the acid that ionized is = (the concentration of [H ] at equilibrium) / (the initial concentration of the acid) * 100 (2.09 x 10-3M / 0.25M) * 100 = 0.84% (i.e. less than 1% of the acid ionized - truly a weak acid) Calculating pH for Solutions of Weak Acids Knowing the starting concentration of a weak acid and the value of the acid dissociation constant, Ka , we can calculate the resulting pH (i.e. [H+]) of the acid solution. The Ka for the dissociation of hypochlorous acid is 3.0 x 10-8. What is the resulting pH of a 0.15M solution of hypochlorous acid? Begin by writing the balanced equation for the dissociation of the acid:

HClO(aq) H+(aq) + ClO-(aq) Now you can write the equilibrium equation for the acid dissociation constant, Ka: Ka = [H+][ClO-] / [HClO]

We know that we started with 0.15M of the acid, but we don't know exactly how much dissociates as it attains equilibrium. So, we will assign the variable X as the amount that dissociates: + From the stoichiometry, if X moles of acid dissociate, then X moles of H are produced, and X moles of conjugate base (i.e. ClO-) are produced We now have a description of the concentrations of the different components at equilibrium: + o [H ] = X o [ClO ] = X o [HClO] = (0.15 - X) These equilibrium values can be plugged into the equilibrium equation:

Ka = 3.0 x 10-8 = [H+][ClO-] / [HClO] = (X * X) / (0.15 - X) Solving for X: (3.0 x 10-8) * (0.15 - X) = X2 X2 + 3.0 x 10-8X - 4.50 x 10-9 = 0 X can be solved using the quadratic equation

This yields two possible solutions for X: X = 6.71 x 10-5, or X = -6.71 x 10-5 + Which is correct? Well, X is supposed to be the [H ], this number cannot be a negative -5 value, so 6.71 x 10 is correct. The pH can be calculated from this value: pH = -log[H+] pH = -log(6.71 x 10-5) pH = -(-4.17) pH = 4.17 A potential shortcut to avoid having to use the quadratic equation for this type of problem: If the initial concentration of weak acid is at least one-hundred fold greater than the value of Ka, then you can assume that the amount that dissociates in going to equilibrium is negligibly small compared to the initial concentration. In this case, the term [INITIAL CONC OF ACID - X] is ~ [INITIAL CONC OF ACID] Let's see if we can apply this shortcut to the above problem: (initial conc)/Ka = (0.15) / (3.0 x 10-8) = 5.00 x 106 This number (5 million) is > 100 therefore we can assume [initial conc of acid - amount that dissociates] ~ [initial conc] Ka = 3.0 x 10-8 = [H+][ClO-] / [HClO] = (X * X) / (0.15 - X) Using the assumption above: (X * X) / (0.15 - X) ~ (X * X) / (0.15) thus -8 3.0 x 10 = (X * X) / (0.15) X2 = 4.5 x 10-9 X = 6.71 x 10-5 Check above and you will see that this number agrees with the answer using the quadratic. The quadratic answer is always accurate, the answer using the shortcut is approximate, but will be reasonably accurate if (initial conc of acid)/Ka > 100

For weak acids, the concentration of [H+] is typically only a small percentage of the total concentration of acid in solution. How does the percentage of acid molecules that ionize vary with the starting concentration of acid? What is the % of Nitrous acid (HNO2) molecules that ionize in a 0.1M and 0.01M solution? (The Ka of nitrous acid is 4.5 x 10-4) The balanced equation for acid dissociation is:

HNO2(aq) H+(aq) + NO2-(aq) The acid dissociation constant is defined as: Ka = [H+][NO2-] / [HNO2]

For a given starting concentration of acid we can set X = the amount of acid that dissociates in attaining equilibrium. From the stoichiometry, X also equals the concentration of [H+] and [NO2-] at equilibrium. Thus: Ka = 4.5 x 10-4 = [H+][NO2-] / [HNO2] = X2/(starting concentration - X) For the 0.1M solution: 4.5 x 10-4 = X2/(0.1 - X) Solve for X using the quadratic equation yields: X = 6.49 x 10-3 = amount of acid dissociated % = (amount dissociated/initial conc) * 100 % = (6.49 x 10-3/0.1) * 100 = 6.49% For the 0.01M solution: 4.5 x 10-4 = X2/(0.01 - X) Solve for X using the quadratic equation yields: X = 1.91 x 10-3 = amount of acid dissociated % = (amount dissociated/initial conc) * 100 % = (1.91 x 10-3/0.01) * 100 = 19.1% There is a 3-fold increase in the number of acid particles that dissociate in response to a 10 fold dilution of the sample. Why is this? A mathematical answer + The percent dissociation is proportional to [H ]/[HA]. From the equilibrium expression we have: Ka = [H+][A-]/[HA] Rearranging: Ka/[A-] = [H+]/[HA] Thus, if [A-] decreases (e.g. as a consequence of dilution) then a proportionally larger concentration of [H+]/[HA] should result An answer based on Le Chatelier's principle We have seen how Le Chatelier's principle can be applied to considerations of concentration, heat, and pressure (i.e. number of molecules). The number of molecules situation might be applied here. The dissociation equilibrium is an equilibrium that involves different numbers of particles for reactant versus product. A shift to the right increases the overall number of particles, a shift to the left decreases the overall number of particles. With regard to the number of particles, dilution would represent a perturbation of the equilibrium due to a net removal of particles (acid, proton and conjugate base). In this case we would predict that diluting the acid would cause the equilibrium to shift in favor of producing more particles (this would cause the reaction to be driven to the right and a greater percentage of acid molecules will dissociate at lower concentration) Polyprotic Acids Many acids have more than 1 ionizable H atom. Such atoms are known as polyprotic acids Sulfurous acid is a polyprotic acid: H2SO3(aq) H+(aq) + HSO3-(aq) Ka1 = 1.7 x 10-2

HSO3(aq) H+(aq) + SO32-(aq) Ka2 = 6.4 x 10-8 Ka1 is the equilibrium constant for ionization of the first proton Ka2 is the equilibrium constant for ionization of the second proton Ka2 is much smaller than Ka1

Its more difficult to remove the second proton. This is because the second proton has to be removed from anegatively charged species (HSO3-) which will have an electrostatic attraction for this second proton It is always easier to remove the first proton from a polyprotic acid (Ka values become successively smaller as protons are removed) Usually Ka values for successive protons in polyprotic acids differ by a value of 103 or greater We can estimate pH values by considering only the Ka1 value for polyprotic acids

WEAK BASES
Weak bases in water react to release a hydroxide (OH-) ion and their conjugate acid: Weak Base(aq) + H2O(l) Conjugate Acid(aq) + OH-(aq) A common weak base is ammonia (NH3). Its conjugate acid is the ammonium ion (NH4+): NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

Since the H2O is the liquid state, and the concentration effectively doesn't change:

Kb is the base-dissociation constant (analogous to the Ka dissociation constant for acids) Kb always refers to the equilibrium in which a base reacts with H2O to form the conjugate acid and OHThe structures of weak bases contain one or more lone pairs of electrons + A lone pair is necessary to form a bond with an H ion (producing the conjugate acid and releasing OH- from H2O) The lone pairs are typically located on Nitrogen atoms in the base

Why Nitrogen? Recall that for weak acids, the atom that the hydrogen is bonded to should have a high electronegativity value that promotes "taking" the shared electrons in the bond with hydrogen. Thus, a hydrogen that is covalently bonded to an oxygen (a highly electronegative element) will loose its electron when ionized (the hydrogen leaves as a proton, H+). In the base structures above we see Nitrogen as the atom bonded to hydrogen. Nitrogen has a lower electronegativity compared to oxygen (but still slightly higher than hydrogen, however). Therefore, any hydrogen that bonds to the nitrogen will exhibit less tendency to ionize and leave as H+. In other words, such compounds tend to accept H+ ions, but don't tend to release them - a characteristic of a base. Elements with electronegativity values lower than hydrogen are all metals. Metal hydrides release hydrogen as the H- ion (the Hydrogen keeps the electrons in the bond). Hydride will react with water to produce OH- and H2(g). Other weak bases are actually the anion forms of weak acids (i.e. the conjugate bases of weak acids)

(note: lone electron pairs to bond with H+ are located on O atoms in this case) Types of Weak Bases How can you tell from the formula whether a compound will behave as a weak base? There are two general categories of weak bases: 1. Neutral compounds containing a non-bonding pair of electrons that can form a bond with a proton (i.e. can function as an acceptor of a proton) o Most of this type of base contains nitrogen (and it's the lone pair on the N that accepts the proton) o These include ammonia (NH3) and related compounds called amines o An amine is like ammonia, exept one or more of the N-H bonds are replaced by a N-C bond. For example, the compound methylamine has the structure:

Amines can extract a proton from H2O by forming a covalent bond with the lone pair of electrons on the Nitrogen atom

2. The second category includes anions of weak acids + o The compound sodium hypochlorite (NaClO) dissociates to yield Na and ClO ions In acid/base neutralization reactions, the Na+ ion would be a spectator ion However, the ClO- ion is the conjugate base of HClO (hypochlorous acid), a weak acid Therefore, the ClO- ion can potentially extract a proton from H2O: ClO-(aq) + H2O(l) HClO(aq) + OH-(aq) o This is the definition of a base, and therefore ClO is a weak base in water Pyridine is a weak base with a Kb = 1.7 x 10-9. What is the pH of a 0.05M solution of pyridine in H2O? C5H5N(aq) + H2O(l) C5H5NH+(aq) + OH-(aq) Kb = [C5H5NH+] [OH-] / [C5H5N] = 1.7 x 10-9 The initial concentration of C5H5N = 0.05M The initial concentration of OH-(aq) is 1 x 10-7M for pure H2O. However, this may be quite small compared to the concentration produced by the ionization of the weak base, so we will ignore it. The initial concentration of C5H5NH+ = 0M

If X M = conc of C5H5N that ionizes, then from the stoichiometry, X M of OH- and X M of C5H5NH+ are produced. Therefore: Kb = 1.7 x 10-9 = [C5H5NH+] [OH-] / [C5H5N] = X2 / (0.05 - X) 8.5 x 10-11 - 1.7 x 10-9X = X2 X2 + 1.7 x 10-9X - 8.5 x 10-11 = 0 This is a quadratic: a = 1, b = 1.7 x 10-9, c = -8.5 x 10-11 X = 0.92 x 10-5M or X = -0.92 x 10-5M X can't be negative, therefore [OH-] = 0.922 x 10-5M pOH = -log(0.922 x 10-5) = 5.04 Recall pH = 14.0 - pOH pH = 14.0 - 5.04 pH = 8.96 This is a basic solution (pH > 7), as expected. Did we have to use the quadratic? Let's assume that the amount that dissociates (X) is small in comparison to the initial concentration (0.05M) Kb = 1.7 x 10-9 = [C5H5NH+] [OH-] / [C5H5N] = X2 / (0.05 - X) X2 / (0.05 ) 1.7 x 10-9 * 0.05 = X2 X = 0.922 x 10-5 This is the same answer from the quadratic. Also, the starting concentration of weak base divided by the value of the Kbis > 100 0.05 / 1.7 x 10-9 = 29,411,764 which is >100 Thus, the shortcut to the quadratic that we saw for weak acid calculations can also be used in weak base calculations

A solution of ammonia (NH3) has a pH of 9.2. The Kb of ammonia is 1.8 x 10-5. What is the molar concentration of the weak base? pOH = 14.0 - pH pOH = 14.0 - 9.2 = 4.8 4.8= -log([OH-]) [OH-] = 1.58 x 10-5 M The balanced equation of the ionization is: NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Therefore, the stoichiometry is such that for each mole of OH- produced, 1 mole of NH3 was ionized, and 1 mole of NH4+ conjugate ion was also produced. If X = starting concentration of ammonia: At equilibrium we have [NH3] = (X - 1.58 x 10-5) [OH-] = 1.58 x 10-5 [NH4+] = 1.58 x 10-5 Kb = 1.8 x 10-5 = (1.58 x 10-5)2 / (X - 1.58 x 10-5) 1.8 x 10-5 = 2.51 x 10-10 / (X - 1.58 x 10-5) X - 1.58 x 10-5 = 2.51 x 10-10 / 1.8 x 10-5 X - 1.58 x 10-5 = 1.40 x 10-5 3.0 x 10-5 M

RELATIONSHIP BETWEEN KA AND KB

Strong acids have weak conjugate bases Strong bases have weak conjugate acids Is there some quantitative relationship between these observations? The ammonia (NH3)/ammonium ion (NH4+) conjugate acid/base pair Ammonia can act as a base and accept a proton in water

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

Ammonium ion can act as an acid and donate a proton in water NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

The two balanced equations for the reaction of NH3(aq) or NH4+(aq) with water can be combined: NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq) NH3(aq) + NH4+(aq) + 2H2O(l) NH3(aq) + H3O+(aq) + NH4+(aq) + OH-(aq) Canceling similar terms on the left and right sides yields: NH3(aq) + NH4+(aq) + 2H2O(l) NH3(aq) + H3O+(aq) + NH4+(aq) + OH-(aq) or

2H2O(l) H3O+(aq) + OH-(aq) or + H2O(l) H (aq) + OH-(aq) Thus, when considering the base/conjugate acid reactions of NH3/NH4+ the combination results in an overall reaction of the ionization of H2O(l) Reaction 1 + Reaction 2 = Reaction 3 Base reaction of NH3 + Conjugate acid reaction of NH4+ = Ionization of H2O We know how to combine reactions to give an overall new reaction - it is the algebraic sum of the reactants and products o But, what is the resulting equilibrium constant for a combined reaction? When two reactions are added to give a third reaction, the equilibrium constant for the overall reaction is equal to the product of the equilibrium constants for the two added reactions K3 = K1 * K2 + For the base reaction of NH3 and the conjugate acid reaction of NH4 , the overall equilibrium constant would be:

In other words, the overall reaction of ammonia with its conjugate acid is the ionization of H2O(l), and the overall equilibrium constant is Kw, the ion-product constant for water This result gives provides a clue as to the relationship between Ka and Kb for acid/conjugate base pairs (or base/conjugate acid pairs): The product of the acid-dissociation constant for an acid (i.e. Ka) and the base-dissociation constant for its conjugate base (i.e. Kb) is the ion-product constant for water Ka * Kb = Kw What are the implications of this relationship? -14 o The product of Ka * Kb must always equal 1 x 10 o If Ka is large (i.e. if the acid is a strong acid), then Kb must be small (i.e. the conjugate base is a weak base) o If Kb is large (i.e. if the base is a strong base), then Ka must be small (i.e. the conjugate acid is a weak acid) In tables of dissociation constants for acids or bases, often only the value for the aciddissociation constants is given. o The base-dissociation constants can be determined from the relationship: Kb = Kw/Ka Also, acid-dissociation constants are sometimes given as pKa values: pKa = -log(Ka) Ka = 10-pKa and pKa + pKb = pKw = 14.0

ACID-BASE PROPERTIES OF SALT SOLUTIONS

Ions can exhibit acidic or basic properties + NH4 can donate a proton (i.e. act as an acid) F can accept a proton (i.e. act as a base) Can salt solutions have acidic or basic properties? Salts are strong electrolytes - they are completely ionized in solution. Any acid or base properties must therefore be due to the properties of their cations or anions Many ions are able to react with H2O(l) to produce H+(aq) or OH-(aq) ions. This is termed Hydrolysis. When weak acids dissociate, they produce anions that are the conjugate base

HA(aq) A-(aq) + H+(aq) The A- ion conjugate base can react with H2O(l) to produce a hydroxide ion, and is therefore a base

A-(aq) + H2O(l) AH(aq) + OH-(aq) The anions of strong acids, by definition, are such weak bases that they do not react with H2O(l) to produce OH-(aq) ions and thus, don't affect the pH of aqueous solutions Amphoteric ions can behave as either an acid or a base HSO3 ions can accept a proton, and behave as a base

HSO3- ions also have a proton they can still donate, thus, they may act as an acid Their behavior in water will be determined by the relative magnitudes of Ka and Kb. Cations All cations, with the exception of group 1 metals, and the heavy group 2 metals (i.e. Ca2+, Sr2+, Ba2+) act as weak acids in aqueous solution Predicting the pH of salt solutions: The ions in a salt represent the spectator ions left over after the neutralization reaction

NaOH(aq) + HCl(aq) Na+(aq) + Cl-(aq) + H2O(l) + o In the above reaction, the cation (Na ) is the conjugate acid of the base NaOH, and the anion (Cl-) is the conjgate base of the acid HCl. + o NaOH is a strong base, and therefore, the conjugate acid (Na ) is so weak as to not have any acidic properties at all o HCl is a strong acid, and therefore, the conjugate base (Cl ) is so weak as to not have any basic properties at all Thus, the salt NaCl is composed of ions that do not have any acid or base properties, and will not affect the pH of an aqueous solution and One can predict whether a salt will have acidic or basic properties by considering the nature of its conjugate acid and base 1. A salt derived from a strong acid and a strong base: As conjugate acid to a strong base and conjugate base to a strong acid both salt ions will be so weak as to have no acid or base properties (see above for NaCl ions) 2. A salt derived from a strong acid and a weak base: The conjugate base to the strong acid (i.e. the anion of the salt) will have no basic properties. The conjugate acid to the weak base (i.e. the cation) will have significant acidic property. Thus, this type of salt in aqueous solution will be acidic in nature. 3. A salt derived from a weak acid and a strong base: The conjugate acid to the strong base (i.e. the cation of the salt) will have no acidic properties. The conjugate base to the weak acid (i.e. the anion) will have significant base property. Thus, this type of salt will be basic in nature. 4. A salt derived from a weak acid and a weak base: The conjugate acid to the weak base (i.e. the cation) will have significant acidic properties and the conjugate base to the weak acid (i.e. the anion) will have significant basic properties. Both cation and anion hydrolyze. The overall affect on pH is dependent upon which is the stronger.

ACID-BASE BEHAVIOR AND CHEMICAL STRUCTURE

How does the chemical structure of a substance determine whether it will behave as an acid, base, or neither? Factors that Affect Strength of Acids and Bases For a molecule to donate a proton, the bond between the molecule and the hydrogen in question must be polarized such that the shared electrons in the bond are attracted away from the leaving hydrogen, and towards the rest of the molecule:

H has an electronegativity of 2.1 and carbon 2.5. This bond is slightly polar, but does not promote withdrawal of the bonding electrons towards carbon. Thus, compounds containing exclusively C-H bonds do not behave as acids