Strong Acids and Bases C020
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1 Strong Acids and Bases C020 Strong Acids and Bases 1 Before discussing acids and bases examine the concept of chemical equilibrium At reaction is at equilibrium when it is proceeding forward and backwards at the same rate, and the concentrations of all species involved remain constant For the following reaction: aa +bb cc + dd K = eq c d [ C] [ D] [ A] a [ B] b ere, [X] rersents the concentration of reactant A (usually in molarity; moles of solute in a litre of solvent; mol L -1 ) and K eq is the equilibrium constant at a given temperature The value of K eq indicates the relative position of the equilibrium; a large K eq means the reaction favours products while a small K eq means the reaction favours reactants. Note that solids do not appear in K eq expressions because their concentrations (densities) are constant Strong Acids and Bases 2 1
2 Start with a General Definition: BrФnsted Acid A BrФnsted definition of an acid is any substance that can donate a + to another substance A + (aq) + A (aq) In water, the association of + with water is so extensive that the solvated species is written 3 + (aq) where 3 + is the hydronium ion. + + δ - Strong Acids and Bases ydronium ion 3 All molecules with a δ+ are capable of acting as acids (e.g. δ+ - δ- R; δ+ -X δ- ) Strong Acids and Bases 4 2
3 BrФnsted Base A BrФnsted definition of an base is any substance that is capable of accepting a + from another substance; (by forming some sort of bond with it). B B or even + + Ḃ. + B All anions are generally good bases: For example: - 2 N - 3 C - Strong Acids and Bases 5 Similarly so are most molecules containing atoms with a lone pair and a partial negative charge. For example: δ - δ - N etc. Strong Acids and Bases 6 3
4 An acid capable of loosing more than 1 is termed a polyprotic acid. In general: For example: 2 S 4 sulfuric acid 2 A (aq) + A - (aq) (acid is 2 A) A (aq) + A 2- (aq) (acid is A - ) Such acids are diprotic Phosphoric acid is an example of a triprotic acid 3 P (aq) +P 3-4 (aq) Strong Acids and Bases 7 A base capable of accepting more than 1 is termed a polyprotic base. For example: C 3 2- carbonate anion C C (base is C 3 2- ) C C (base is C 3- ) Strong Acids and Bases 8 4
5 It is not unusual for a single substance to be able to function as either an acid or a base. These are called amphiprotic substances For example: S S 4 2- (acid is S 4- ) S S (base is S 4- ) Therefore, S 4- is amphiprotic Strong Acids and Bases 9 The most common amphiprotic substance is 2 which can autoionize: 2 (l) + 2 (l) 3 + (aq) + - (aq) acid base For this reaction, the equilibrium constant K is given by: K = + [ ][ ] 3 [ ] 2 But in dilute solution [ 2 ] 2 ~ constant Therefore: K[ 2 ] 2 = K W water ionization constant At 25 o C, K W = x ~ Strong Acids and Bases 10 5
6 Therefore: K W = [ 3 + ][ - ] = 1.0 x This leads to the concept of p and p Since in pure neutral water [ 3 + ][ - ] = 1.0 x and [ 3 + ] = [ - ] = 1.0 x 10-7 mol L -1 water is arbitrarily accepted as the measure of neutrality for defining acids and base. If [ 3 + ] > 1.0 x 10-7 M, the solution is said to be acidic If [ 3 + ] < 1.0 x 10-7 M, the solution is said to be basic Strong Acids and Bases 11 [ 3 + ] and [ - ] are usually given as simple numbers instead of exponents by using the following conversions: p = -log 10 [ 3 + ] Example: and p = -log 10 [ - ] Given [ 3 + ] = M p = -log 10 (3.57 x 10-3 ) =2.45 Given [ - ] = 3.0 x 10-7 M p = -log 10 (3.0 x 10-7 ) = 6.52 Strong Acids and Bases 12 6
7 You can work backwards too. For example: If p = 2.49 [ 3 + ] = = 3.24 x 10-3 M If p = 9.08 [ - ] = = 8.32 x M Strong Acids and Bases 13 For neutral water at equilibrium [ 3 + ] = [ - ] = 1.0 x 10-7 M p = p = 7.0 Q K W = [ 3 + ][ - ] -log 10 (K W )=-log 10 ([ 3 + ][ - ]) = -log 10 ([ 3 + ]) log 10 ([ - ]) pk W = p+p = 14 Note: p or p can be negative for very high concentrations Strong Acids and Bases 14 7
8 Example: What will be the p and p of a solution where 0.73 g Cl are dissolved In 100 ml of 2? Cl is a strong acid and therefore fully dissociated. [ 3 + ]=[Cl] o = initial concentration of hydrochloric acid 0.73g [ Cl] o = = 0.20M 1 (0.1L)(36.5g mol ) p = -log 10 (0.2) = 0.7 and p = = 13.3 Strong Acids and Bases 15 Strong Acids and Bases 16 8
9 Conjugate Acid/Base Pairs Acids and base reactions are complementary reactions; that is, they must always occur together For example: δ - δ - -Cl + N- N Cl - acid base conjugate acid In general: A + B B + + A - acid base conjugate acid conjugate base conjugate base Strong Acids and Bases 17 After an acid loses a proton it becomes a substance capable of accepting the proton back again; that is, an acid is transformed into its conjugate base by loss of a proton. Similarly, after a base accepts a proton it becomes a substance capable of donating a proton; that is, a base is transformed into is conjugate acid by gain of a proton. Example: For each of the following: i) State whether the substance is an acid, base or amphiprotic ii) Underline the acidic or encircle the basic atom iii) Draw the structure of the conjugate acid/base Strong Acids and Bases 18 9
10 a) δ - N + + N base conjugate acid b) 3C C acid δ - δ+ + 2 C 3C conjugate base Strong Acids and Bases 19 c) C + + C base conjugate acid d) C δ- + + C conjugate acid amphiprotic + 2 C conjugate base Strong Acids and Bases 20 10
11 Strong Acids and Bases (Weak acids and Bases later) For the ionization of all acids; that is: A A - the concentration of all species at equilibrium is given by: K = + [ ][ A ] 3 [ A][ ] and since in aqueous solution [ 2 ]~ constant, one writes: K[ 2 ]=K a = acid ionization constant + [ 3 ][ A ] K a = 2 [ A] Strong Acids and Bases 21 K a is a measure of acid strength and pk a = -log 10 K a If at equilibrium [ 3 + ][A - ] >> [A] then K a >> 1 and pk a << 1 The acid is then said to be a strong acid Strong acids are fully dissociated in water. There are six common strong acids: Cl, Br, I, N 3, Cl 4 and 2 S 4 (first ionization only) All strong acids A will dissociate completely to 3 + and A - [ 3 + ] = initial concentration of A = [A] o Strong Acids and Bases 22 11
12 For the ionization of all bases: B B + - The concentration of all species at equilibrium is given by: K = Again since [ 2 ] ~ constant: K [ ] 2 [ B][ ] [ B ][ ] = K b = 2 [ B][ ] [ B ] where K b = base ionization constant and pk b = -log 10 K b Strong Acids and Bases 23 Strong bases correspond to the case where [B][ - ] >> [B - ] and K b >> 1 All species containing -, and molecules with atoms having a negative charge will be strong bases. For example: Li, Na, K, Ca() 2, Sr() 2, Ba() 2, 3C-, 2 N -, etc. All halogen ions, X - = F -, Cl -, Br -, I -, and neutral atoms with a lone pair of electrons will be weaker bases A strong base B will react completely with water to form B and - at equilibrium [- ] = initial concentration of base = [B] o Strong Acids and Bases 24 12
13 Acids and bases react to form a salt and water For example: A + Na Na + A p Indicators Many natural substances change color when they change from acid to conjugate base These substances can be used as indicators of acidic and basic solutions For example: let an indicator molecule = In In In - Color A Color B In acid solution the indicator will show color A and in basic solution, color B The change in color occurs over a range of p values (usually 2) but can occur quite suddenly when the p changes rapidly during a titration. Strong Acids and Bases 25 13
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