Chapter 14 Notes
Chapter 14 Notes
p.1
14.1 The Nature of Acids and Bases Arrhenius concept of acids and bases: acids produce H+ in aqueous solution; bases produce OH-. This was ground-breaking at the time but limited to aqueous systems and bases with hydroxide only. Brnsted-Lowry model: an acid is a proton donor (H+); a base is a proton acceptor HA (aq) + H2O (l) H3O+ (aq) + A- (aq) acid base conjugate acid conjugate base
conjugate base is everything left of the acid molecule after the proton is lost the conjugate acid is formed when a proton is transferred to the original base conjugate acid-base pair consists of two substances related to each other by the donating and accepting of a single proton there is a competition for the proton between the two bases: H2O and A-. The strength of the bases affects the equilibrium position!
o Ka is the acid dissociation constant o the proton can be written as either H+ or H3O+ o [H2O] is not included in the expression because it is a pure liquid, which is
dissociation of an acid: HA H+ + A- and Ka is used for both reactions do Sample Exercise 14.1 (especially part e!!)
essentially constant
Brnsted-Lowry is not limited to aqueous phase reactions! Here is another B-L acidbase reaction: NH3 (g) + HCl (g) NH4Cl (s) In this case, HCl has donated a proton to NH3 to make NH4+ and Cl-.
14.2 Acid Strength The strength of an acid is defined by the equilibrium position of the dissociation (ionization) reaction: HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
strong acid: equilibrium lies far to the rightalmost all the acid is ionized and Ka is very large. A strong acid has a weak conjugate base: the base has a low affinity for the proton. We can say that a strong acid has a conjugate base that is much weaker than water (water molecules win the competition for H+ ions). weak acid: the equilibrium lies far to the left; most of the acid is still present as HA and Ka is very small. Weak acids have strong conjugate basesmuch stronger than water. o strong acids: H2SO4 (*), HCl, HNO3, HClO4 o *note that for H2SO4, the first dissociation is very strong: H2SO4 H+ + HSO4- but the second dissociation is very weak: HSO4- H+ + SO42o weak acids: H3PO4, HNO2, HOCl, CH3COOH (acetic acid, also written as HC2H3O2), C6H5COOH (benzoic acid)
Gano Fall 08
p.2
oxyacids: the acidic proton is attached to an oxygen atom (there are both weak and strong oxyacids) organic acids: these contain a carbon atom backbone, and commonly contain a carboxyl group: COOH. These are usually weak acids. The only acidic proton is the one in the carboxyl group. hydrohalic acids: the acidic proton is attached to a halide ion (HX).
Sample Exercise 14.2 Arrange the following according to base strength: H2O, F-, Cl-, NO2-, CNHCl is a very strong acid, so Cl- is the weakest base. H2O is a stronger base than the conjugate base of a strong acid (like Cl-) but weaker than the conjugate base of a weak acid (like F-). For the others, compare the Ka for the acid to determine base strength. So the correct order is: weakest= Cl- < H2O < F- < NO2- < CNamphoteric: can behave as either an acid or a base. Water is the most common amphoteric material, and can actually autoionize: H2O + H2O H3O+ + OHOne water molecule is acting as a base, and the other is acting as an acid! (Liquid ammonia can also autoionize: 2NH3 (l) NH4+ + NH2-) o we can write an equilibrium expression for water: Kw = [H3O+][OH-] where Kw is the ion-product constant or dissociation constant for water o at 25C in neutral water, [H3O+] = [OH-] = 1 x 10-7 M so Kw = 1 x 10-14 o this is true for ANY aqueous solution! do Sample Exercise 14.3 Sample Exercise 14.4 a) at 60C, Kw = 1 x 10-13. Use LeChateliers Principle to determine if the reaction 2H2O H3O+ + OH- is exothermic or endothermic. We have added heat (from 25C) and the Kw has gotten larger, so the reaction has shifted to the right, making a larger concentration of ions. So it must be using up excess heat, and the reaction is therefore endothermic. b) [H3O+] = [OH-] =
1x10
13
14.3 The pH Scale pH = -log[H+] sig figs: the number of decimal places in the log equals the number of sig figs in the original number!! ex: [H+] = 1.0 x 10-9 pH = 9.00 2 sig figs 2 decimal places!! pH = 3 is 10x more concentrated than pH = 4; 100x more than pH = 5!! do Sample Exercises 14.5 and 14.6 14.4 Calculating the pH of Strong Acid Solutions A strong acid completely dissociates in aqueous solution. in order to calculate the pH, we can ignore the contribution of H+ from the autoionization of water. do Sample Exercise 14.7 14.5 Calculating the pH of Weak Acid Solutions
Gano Fall 08
p.3
[H + ][F [H ] F
Use an ICE chart as we did before for equilibrium problems: HF 1.00M -x 1.00-x
H+ 0 +x x
F0 +x x
[x ] ][x [1 - x ]
4.
Check the reasonableness of the answer: Ka values are typically known to + 5%. If x is less than 5% of [HA]0, then it is reasonable to have ignored it. Since
2.7x10 1
5.
Find pH: pH = -log[H+] = -log(2.7 x 10-2) = 1.57 Sample Exercise 14.8 Calculate the pH of a 0.100M solution of hypochlorous acid, HOCl, Ka = 3.5 x 10-8 HOCl H+ + OCl- this is a larger effect than waters autoionization.
H+ 0 +x x
OCl0 +x x
[x][x] [0.1 - x]
x2 = 3.5 x 10-8 and x = 5.9 x 10-5 = [H+] 0 .1 5.9x10 5 Check that our assumption was valid: x100% = 0.59%, which is much less 0.1
than 5%! So [H+] = 5.9 x 10-5 and pH = 4.23 Sample Exercise 14.9 pH of Weak Acid Mixtures
Gano Fall 08
p.4
H+ 0 +x x
NO20 +x x
[x ] ][x [5 - x ]
x2 = 4.0 x 10-4 and x = 4.5 x 10-2 = [H+] 5 4.5x10 2 Check that our assumption was valid: x100% = 0.90%, which is much less 5
So Ka = than 5%! So [H+] = 4.5 x 10-2 and pH = 1.35 Now we can find [CN-], which is affected by the H+ released by HNO2: HCN H+ CNInitial 1 4.5 x 10-2 0 Change -x +x +x Equilibrium 1-x 4.5 x 10-2 +x x But again we can assume that x is very small as compared to x and compared to 4.5 x 10-2 (according to LeChatelier, having H+ ions in solution causes equilibrium to shift to the left AND the acid is very very weak). So Ka = 6.2 x 10-10 = [CN-] = 1.4 x 10-8 M, which is 106 times smaller than [H+]
percent dissociation: the amount of a weak acid that has dissociated in achieving equilibrium. % dissociation =
For our previous example with HF, [H+] = 2.7 x 10-2 M and the starting concentration was 1.00 M. So % dissociation =
For a given weak acid, the percent dissociation increases as the acid becomes more
dilute!!! Sample Exercise 14.10 Calculate the % dissociation for acetic acid (Ka = 1.8 x 10-5) for each:
Gano Fall 08
p.5
H+ 0 +x x
C2H3O20 +x x
Assume that x << 1, so Ka = 1.8 x 10-5 = So x = [H+] = 4.2 x 10-3 M b) 0.1 M HC2H3O2 HC2H3O2 0.1 -x 0.1-x
and % dissociation =
H+ 0 +x x
C2H3O20 +x x
and % dissociation =
We can get a general trend from this problem o for any weak acid HA, [H+] decreases and [HA]0 decreases o for any weak acid HA, % dissociation increases as [HA]0 decreases o this occurs because diluting an acid causes the equilibrium to shift to the right, towards more ions. Although the actual amount of ions produced is fewer, the percent of the original acid is greater!! Read Household Chemistry, p 679. Understand hypochlorite equilibrium!!! Sample Exercise 14.11 In a 0.100 M solution of lactic acid (HC3H5O3), the acid is 3.7% dissociated. Calculate Ka. % dissociation = [HC3H5O3] = 0.1 x = 0.1 [C3H5O3-] = [H+] = .0037 14.6 Bases
strong bases: completely dissociate in aqueous solution. All hydroxides of Group I elements are strong bases (the ones besides NaOH and KOH are expensive, so are not used much in lab). Hydroxides of Group II (alkali earth) elements are also strong but are not very soluble.
Gano Fall 08
p.6
Low solubility prevents large OH- concentrations in the mouth, esophagus, or stomach. But there are plenty of OH- ions available, and as the neutralization proceeds, more of the salt dissolves. o Ca(OH)2 is called slaked lime and is used to neutralize SO2 from power plant exhausts (remember the section on acid rain?). o lime-soda process is used to soften water. Lime (CaO) and soda ash (Na2CO3) are added to water: CaO (s) + H2O Ca(OH)2 (aq) 2+ Ca(OH)2 (aq) + Ca (aq) + 2HCO3- (aq) 2CaCO3 (s) + 2H2O (l) Ca2+ comes from hard water; HCO3- comes from soda ash + water do Sample Exercise 14.12
many proton acceptors dont contain OH-, but when in water, they increase [OH-]: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) base acid conj. acid conj. base o these bases usually have one unshared pair of electrons that can bond with a proton. This often (but not always) happens with nitrogen:
methylamine CH3NH2 dimethylamine (CH3)2NH trimethylamine (CH3)3N ethylamine C2H5NH2 N pyridine all have the structure X N : X X
form a conjugate acid and hydroxide. Bases like B must always compete with OH-, a very strong base, for H+. So Kb is small and they are usually weak bases. Sample Exercise 14.13 Calculate the pH for a 15.0 M solution of NH3 (Kb = 1.8 x 10-5). Both ammonia and water produce [OH-]: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) Kb = 1.8 x 10-5 + H2O H + OH Kw = 1 x 10-14 But since Kb >> Kw, the equilibrium for ammonia will dominate: Kb =
= 1.8 x 10-5
NH4+ 0 +x x
OH0 +x x
Gano Fall 08
p.7
[x][x] x2 = = 1.8 x 10-5 and x = 1.6 x 10-2 = [OH-] [15 - x] 15 Kw 1x10 14 = [H+] = = 6.3 x 10-13 So pH = 12.20 [OH ] 1.6x10 2
Kb =
we could have calculated pH from pOH = -log[OH-] and pH + pOH = 14 ammonia bottles are often labeled NH4OH, but you can see that very little of the
NH3 actually dissociates into NH4OH!! (1.6 x 10-2 / 15 = 0.11%) do Sample Exercise 14.14 (another base example)
14.7 Polyprotic Acids polyprotic acids can furnish more than one proton. They dissociate in a stepwise wayone proton at a time! H2CO3 (aq) HCO3 (aq)
-
the conjugate base of the first dissociation becomes the acid in the second step Ka1 > Ka2 -- it gets harder to remove each successive proton. As the negative charge on the acid increases, it gets hard to remove a positive proton! for an acid like phosphoric, H3PO4, the first dissociation is so much larger than the second or third that its the only one that has an effect on pH
Sample Exercise 14.15 Calculate the pH of a 5.0 M H3PO4 solution and concentrations of H3PO4, H2PO4-, HPO42-, and PO43-. The main effect is the dissociation of H3PO4: H3PO4 (aq)
[H + ][H 2 PO ] 4 [H 3 PO 4 ]
H2PO40 +x x
[x ] ][x [5 - x ]
x2 5
so pH = 0.72
(0.19)[HPO (0.19)
2 4
Gano Fall 08
p.8
[H + ][PO 3 ] 4 [HPO 2- ] 4
(0.19)[HPO 2 ] 4 (6.2 x 10 -8 )
we can see that the concentrations of all species are extremely LOW
sulfuric acid is unique because it is a strong acid in the first dissociation and a weak
acid in the second dissociation! H2SO4 (aq) H+ (aq) + HSO4- (aq) HSO4- (aq) H+ (aq) + SO42- (aq) Ka1 is very large Ka2 = 1.2 x 10-2
Sample Exercise 14.16 Calculate the pH of a 1.0 M solution of H2SO4. The major species in solution are H+, HSO4-, and H2O. The concentration of H+ is at least 1.0 M, from the first dissociation. But does HSO4- dissociate enough to also produce H+? HSO41.0 -x 1-x
H+ 1.0 +x 1+x
SO420 +x x
so x = 1.2 x 10-2
Since x is only 1.2% of 1.0, we made a good assumption to disregard x in comparison to 1.0. So [H+] = 1.0 + 1.2 x 10-2 = 1.0 to the correct sig figs. So the dissociation of HSO4does not contribute greatly to [H+]. So [H+] = 1.0 and pH = 0.00!! But if the initial concentration of H2SO4 is less than 1.0 M, then the second dissociation does have an effect, and the problem needs to be solved with the quadratic equation. Sample Exercise 14.17 Calculate the pH of a 1.0 x 10-2 M solution of H2SO4. HSO40.01 -x 0.01-x
H+ 0.01 +x 0.01+x
SO420 +x x
If we make the approximation that x < 0.01, we get the result of x = 0.012, which is greater than 0.01! So we must solve using the quadratic, and we get x = 4.5 x 10-3 M. So [H+] = 0.01 + 4.5 x 10-3 = 0.0145 M and pH = 1.84
Gano Fall 08
p.9
KEY POINTS 1. Usually, successive Kas are so much smaller than the first value that only the first one has an effect on [H+]. The calculation for pH for a weak polyprotic acid is identical to that for a weak monoprotic acid! 2. For concentrated solutions of H2SO4 (1.0 M or greater), the large [H+] from the first step represses the second step, which can be neglected. For dilute solutions, the second step contributes and the quadratic equation must be used. 14.8 Acid-Base Properties of Salts salt is an ionic compound
salts that consist of cations of strong bases and anions of strong acids have NO effect on [H+] when dissolved in water! For example, aqueous solutions of KNO3, KCl, NaCl, and NaNO3 are all neutral. This is because Cl- and NO3- are anions of strong acidsthey dont combine with H+. Likewise, K+ and Na+ dont combine with OH-. for any salt whose anion is the conjugate base of a weak acid, the aqueous solution will be basic. For example, sodium acetate, NaC2H3O2: Na+ is the cation of a strong base, so it wont recombine with OH-. But C2H3O2- is the anion of a weak acid, so it acts as a conjugate base! C2H3O2- + H2O
HC2H3O2 + OH-
Kb =
[OH - ][HC 2 H 3 O 2 ] [C 2 H 3 O 2 ]
= [H+][OH-]
we know that for acetic acid Ka = 1.8 x 10-5. We can actually determine Kb: Ka x Kb =
So Ka x Kb = Kw!!
Sample Exercise 14.18 Calculate the pH of a 0.30 M solution of NaF. Ka for HF = 7.2 x 10-4 In solution, we will have Na+, F-, and H2O. HF is a weak acid, so F- is a strong conjugate base. F- + H2O HF + OHKb = Kw/Ka = 1 x 10-14/7.2 x 10-4 = 1.4 x 10-11 Kb =
[HF][OH [F - ]
= 1.4 x 10-11
F0.30 -x 0.30-x
OH0 +x x
HF 0 +x x
So pOH = 5.69
we must be very careful looking at base strength!! Think about HCN, another weak acid: HCN + H2O CN- + H3O+ Ka = 6.2 x 10-10
Gano Fall 08
AP Chemistry: Zumdahl Notes o looking at this, CN- appears to be a relatively strong conjugate base, and o
p.10
compared to H2O, has a strong affinity for H+ but, when CN- is in water (from the dissolution of a salt like NaCN, for example), you get the reaction CN- + H2O HCN + OH- and CN- is only a weak base (Kb = Kw/Ka = 1 x 10-14/6.2 x 10-10 = 1.6 x 10-5). This is because, in this case, CN- is competing with OH-, a very strong base, for H+. so in terms of base strength, OH- > CN- > H2O
salts with a cation which is the conjugate acid of a weak base produce acidic solutions. NH4Cl, for example, produces NH4+ and Cl-. Cl- will not recombine with H+, but NH4+ will donate a proton easily to make NH3 + H3O+ Sample Exercise 14.19 Calculate the pH of a 0.10 M NH4Cl solution. Kb for NH3 = 1.8 x 10-5 NH4+ NH3 + H+ Ka = Kw/Kb = 1 x 10-14/1.8 x 10-5 = 5.6 x 10-10
NH3 0 +x x
H+ 0 +x x so pH = 5.13
highly charged metal ions polarize the OH bonds in the water molecules that get attached to them, making those water molecules more acidic. The higher the charge on the metal ion, the stronger the acidity of the hydrated ion!! Sample Exercise 14.20 Calculate the pH of 0.01 M AlCl3 solution. Ka for Al(H2O)63+ is 1.4 x 10-5 Al(H2O)63+ 0.01 -x 0.01-x
Al(OH)(H2O)52+ 0 +x x
H+ 0 +x x so pH = 3.43
[x][x] x2 = [0.01 - x] 0 1 .0
what happens if you have something like NH4C2H3O2 where both the weak acid and
weak base can form? Qualitatively: o if Ka for the acidic ion > Kb for the basic ion, then the solution will be acidic o if Kb > Ka, the solution will be basic o if Ka = Kb, the solution will be neutral!
Gano Fall 08
p.11
Ka for NH4+ = 5.6 x 10-10 Kb for C2H3O2 = 5.6 x 10-10 Ka = Kb so neutral + -10 b) NH4CN Ka for NH4 = 5.6 x 10 Kb for CN- = 1.6 x 10-5 Kb >> Ka so basic 3+ -5 c) Al2(SO4)3 Ka for Al(H2O)6 = 1.4 x 10 Kb for SO42- = ? HSO4- is a conjugate acid for SO42-, and its Ka is Ka2 for H2SO4, or 1.2 x 10-2. So Kb = Kw/Ka = 1 x 10-14/1.2 x 10-2 = 8.3 x 10-13 Ka >> Kb so acidic See Table 14.6 for a summary!! 14.9 The Effect of Structure on Acid-Base Properties What determines if a substance XH will donate a hydrogen? - strength of the bond - polarity of the bond Even though the HF bond is very polar, it is a weak acid because the HF bonds are also very strong.
oxyacids have the form HOX **Acid strength increases with an increase in the number of oxygen atoms attached!! This happens because oxygen is so electronegative, and it draws electrons away from the central atom and the OH bond. This polarizes and weakens the OH bond, making the H easier to lose. Also, the more electronegative X is, the stronger the acid!! Sulfuric acid is therefore stronger than sulfurous acid because the extra oxygen leads to a more polar SO bond. See Tables 14.8 and 14.9 for a summary!!
this is also true for hydrated metal ions. Highly charged metals (like Al3+) produce acidic solutions because electrons are attracted to the highly positive metal ion: Al 3+ O H H
becomes weakly attached
e-
14.10 Acid-Base Properties of Oxides If a molecule contains HOX, it can be acidic and release a hydrogen. But, it could also be basic and produce OH-, if the bonds break right! The key is the OX bond: if X is very electronegative, the OX bond is covalent and strong. The bond will be polar and the relatively weak HO bond will break, releasing a proton.
if X has low electronegativity, the OX bond is ionic and easily broken in water, releasing OH-: NaOH, KOH when a covalent oxide like SO3 is dissolved in water, you get an acidic solution: SO3 (g) + H2O (l) H2SO4 (aq) O OS bonds are strong and covalent HO bonds are weaker, break easily S H O O H
Gano Fall 08
p.12
when a covalent oxide dissolves in water, an acidic solution forms. These are acid oxides: SO2 (g) + H2O (l) H2SO3 (aq) CO2 (g) + H2O (l) H2CO3 (aq) 2NO2 (g) + H2O (l) HNO3 (q) + HNO2 (aq) when an ionic oxide dissolves, a basic solution forms. These are basic oxides: CaO (s) + H2O (l) Ca(OH)2 (aq) K2O (s) + H2O (l) 2KOH (aq)
14.11 The Lewis Acid-Base Model Lewis acid: an electron-pair acceptor; has an empty atomic orbital that it can use to accept an electron pair Lewis base: an electron-pair donor; has a lone pair of electrons that it can donate H+ + :NH3 NH4+
H+ + :O-H : : : : : : H2O
A key example is BF3 + :NH3 BF3NH3 - BF3 is the Lewis acid - :NH3 is the Lewis base Another example is aluminum metal:
: Al 3+ + 6 O :
H H
[ (
Al
:
)] H
6
3+
do Sample Exercise 14.22 14.12 Strategy for Solving Acid-Base Problems: A Summary READ THIS!!!
Gano Fall 08