Acid-Base Properties of Salt Solutions and Acid-Base Strength

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1 AcidBase Properties of Salt Solutions and AcidBase Strength A salt is simply another name for an ionic compound. Remember, that most salts are strong electrolytes that completely dissociate in solution. By dissociation, salts can sometimes affect ph by increasing H + or OH concentrations, donating or accepting a proton, in side reactions. The reactions of ions with water are frequently called hydrolysis reactions. For Example: NaF (s) Na + (aq) + F (aq) No apparent change in ph; However, F + H 2 O HF + OH Salts that form Neutral Solutions We know from the Bronsted Lowry theory that conjugate bases of strong acids have no affinity for protons in water. Example: HNO 3 + H 2 O H 3 O + + NO 3 If NO 3 had any affinity for H +, then this reaction would be an equilibrium reaction. By this logic, we should understand that the addition of salts containing cations of strong bases and anions of strong acids have no effect on the ph of a solution. i.e. AgNO 3 Ag + + NO 3 Salts That Form Basic Solutions Notice what happens when we put sodium acetate in solution NaCH 3 CO 2 Na + + CH 3 CO 2 And then, CH 3 CO 2 + H 2 O CH 3 CO 2 H + OH What happed to the ph when the sodium acetate was added? 1

2 In this situation, the acetate anion is acting as a weak base. Because we know the K a of the conjugate acid, acetic acid, we can easily calculate the K b of the acetate anion from: K b = K w / K a = 1.0x10 14 / 1.8x10 5 = 5.6x10 10 By knowing the dissociation constant, we can now make calculations of the solution knowing the initial concentration. 1. What is the ph of a solution made by adding 3.0 g of sodium acetate to make 5.0 L solution? Notice, the solution is very basic. Salts derived from a strong base and a weak acid create basic solutions. Examples: NaClO, LiF, etc Salts That Form Acidic Solutions Observe: NH 4 Cl + H 2 O NH 4+ + Cl And then, NH 4+ + H 2 O NH 3 + H 3 O + So, we see that salts derived from a weak base and strong acid create acidic solutions A second type of salt that produces an acid solution is one that contains a highly charged metal ion. i.e. Al The presence of aluminum ions in solution results in the formation of coordination bonds between the ion and unshared pairs of electrons on the water molecules These compounds are known as metal hydrates. Because metal ions are positively charged, they attract the unshared electron pairs of water molecules. Notice, Aluminum is of the third period and can have an expanded octet. It has accepted 6 coordination bonds. Now, Look at Fe Fe + 6H 2 O Fe(H 2 O) 6 What definition best describes the formation of a metal hydrate? Al(NO 3 ) 3 Al(H 2 O) 6 + NO 3 Draw the orbital notation for Al 2

3 When a water molecule interacts with the positively charged metal ion, electron density is drawn from the oxygen causing the OH bond to become more polarized; as a result, water molecules bound to the metal ion act as a source of protons: Al(NO 3 ) 3 + 6H 2 O Al(H 2 O) 6 + NO 3 Al(H 2 O) 6 Al(OH)(H 2 O) H + Al(H 2 O) 6 Al(OH)(H 2 O) H + From a known K a value, the ph for solutions containing hydrated ions can be easily calculated. 2. Calculate the ph and poh of a 1.0x10 4 M AlCl 3 solution. Metal Hydrates increase in their acid strength as their charge increases and atomic radius decreases Fe is a fairly strong acid compared to Al Fe + 6H 2 O Fe(H 2 O) 6 Ka = 2.0x10 3 Wow, metal ions act as Acids! Except, in most cases, Heavy Group I and Group II metals. Salts of binary hydrides (HS ) and polyprotic oxyacids often have anions that can form salts that are amphoteric. Example: anions of PO 4 PO 4 3 (BL Base) H 2 PO 4 2 (BL Acid or Base) Therefore, NaH 2 PO 4 could be acidic or basic depending on relative K a and K b values 3

4 3. Predict whether Na 2 HPO 4 will be acidic or basic in aqueous solution. 4. Determine if the following salts will result in a neutral, acidic, or basic solution when dissolved a. Ammonium acetate b.lithium chloride c. Iron (II) sulfate d.ammonium fluoride e. Lithium phosphate Acid and Base Strength Strong acids are completely dissociated in water. Their conjugate bases are quite weak. Weak acids only dissociate partially in water. Their conjugate bases are stronger bases. Acid and Base Strength In any acidbase reaction, the equilibrium will favor the reaction that moves the proton to the stronger base. HCl (aq) + H 2 O (l) H 3 O + (aq) + Cl (aq) H 2 O is a much stronger base than Cl, so the equilibrium lies so far to the right K is not measured (K>>1). Acid and Base Strength HC 2 H 3 O 2(aq) + H 2 O (l) H 3 O +(aq) + C 2 H 3 O 2 (aq) Acetate is a stronger base than H 2 O, so the equilibrium favors the left side (K<1). It is important to remember that a chemical species does not simply want to give up a proton. The intermolecular forces of all substances in the mixture must favor the result of a H + being moved from one species to another. Factors affecting acid strength: 1. Electronegativity 2. Bond Strength 3. Stability of the conjugate base 4

5 For any molecule XH, the H + can only be removed if X has a high enough electronegativity to retain both electrons across the bond. For hydrohalic acids, notice the difference in electronegativities: 2.1 H F H Cl H Br H I 2.5 The more polar the H X bond and/or the weaker the H X bond, the more acidic the compound. So acidity increases from left to right across a row and from top to bottom down a group Pearson Education, Inc. So: However: HCl H + + Cl HF H + + F Very polar bond! Stable conjugate base What could cause HF to be a weak acid? Hydride acids tend to all be weak acids due to their low difference in electronegativies in relationship to the hydrogen atom. The more electronegative, the stronger. C 2.5 Si 1.8 N 3.0 P 2.1 As 2.0 O 3.5 S 2.5 Se 2.4 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5 Oxyacids Given the general formula: X O H If X is a metal, it is easier to dissociate the X O bond; therefore the compound would be a base Oxyacids increase in strength with the increasing electronegativity of the central atom Strength: H 3 PO 4 < H 2 SO 4 < HNO 3 For oxyacids with the same central atom, acid strength increases with an increase in the number of oxygen's If X is a nonmetal, it is easier to dissociate the O H bond; therefore the compound would be an acid 5

6 For ployprotic acids, each successive proton requires more energy to remove; therefore, the lower the acid strength becomes Resonance in the conjugate bases of carboxylic acids stabilizes the base and makes the conjugate acid more acidic. Strength: H 1+ > H 2+ > H > etc 5. Identify the stronger of the following acid or base pairs: a. HIO 3, HBrO 3 b.hno 2, HNO 3 c. H 2 S, H 3 P d.hf, HI e. Li 2 O, CH 3 CH 2 CH 2 NH 2 f. H 2 PO 3, HPO 3 2 6

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