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CHEMISTRY LECTURE

CHEMISTRY LECTURE

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5) you would have to take to prepare 100 mL of a buffer at pH 10.00 if the final salt concentration is to be 0.200 M. kb = 1.75x10-5

Solution The key to solving any problem is the equilibrium of substances in solution.

Here, we have ammonia and ammonium which are combined in the equation: NH3 + H2O D NH4+ + OHKb = [NH4+][OH-]/[NH3] We are aware of the pH which means that we can find [OH] and we are given the concentration of NH4+ as 0.200 M. Therefore: pOH = 14 10 = 4 [OH-] = 10-4 M Now we can solve the equilibrium relation to find [NH3] 1.75x10-5 = (0.200x 10-4)/[NH3] [NH3] = 1.14 M

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We need 100 mL of 1.14 M to be prepared from 14.8 M so we have mmol ammonia needed = 1.14x100 = 114 mmol mL ammonia = mmol/molarity = 114/14.8 = 7.7 mL Or simply, MiVi = MfVf 14.8* VmL = 1.14 * 100 VmL = 7.7 mL The weight of NH4Cl can also be found as the volume and molarity are given in the problem Mmol NH4Cl = 0.200 x 100 = 20.0 mmol Mg NH4Cl = 20.0 x 53.5 = 1070 mg

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Example How many g ammonium chloride (FW = 53.5) and how many mL of 3.0 M NaOH should be added to 200 mL water and diluted to 500 mL to prepare a buffer at pH 9.5 and a salt concentration of 0.10 M.

Solution Once again, the key to solving this problem is the equilibrium of substances in solution.

Here, we have ammonia and ammonium which are combined in the equation NH3 + H2O D NH4+ + OHKb = [NH4+][OH-]/[NH3]

We are aware of the pH which means that we can find [OH-] and we are given the concentration of NH4+ as 0.10 M. Therefore: pOH = 14 9.5 = 4.5 [OH-] = 10-4.5 = 3.2x10-5 M

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Now we can solve the equilibrium relation to find [NH3] 1.75x10-5 = 0.10 x 3.2x10-5/[NH3] [NH3] = 0.18 M mmol NH3 = 0.18 x 500 = 90 mmol mmol NaOH = mmol ammonia VmL NaOH = mmol/molarity = 90/3.0 = 30 mL mmol NH4+ = 0.10 x 500 = 50 mmol Total mmol salt = mmol ammonia + mmol ammonium = 90 + 50 = 140 mmol mg NH4Cl = 140 x 53.5 = 7.49x103 mg = 7.49 g

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Solutions of Polyprotic Acids Polyprotic acids are weak acids, except sulfuric acid where the dissociation of the first proton is complete, which partially dissociate in water in a multi step equilibria where hydrogen ions are produced in each step. Examples include carbonic, oxalic maleic, phosphoric, etc. A general simplification in the calculation of pH of such acids is to compare ka1 and ka2 where ,usually ka1/ka2 is a large value (>104) and thus equilibria other than the first dissociation step can be ignored.

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Let us look at the following example: H3PO4 D H+ + H2PO4ka1 = 1.1 x 10-2 H2PO4- D H+ + HPO42ka2 = 7.5 x 10-8 HPO42- D H+ + PO43ka3 = 4.8 x 10-13 [H+] = [H+]H3PO4 + [H+]H2PO4- + [H+]HPO4Looking at the values of the acid dissociation constants for the three steps, it is obvious that the first step occurs about 106 times greater than the second and thus the amount of protons in the second step is negligible ( [H+]H2PO4- ) compared with the first.

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In addition, the third step comes from the second step and since the second step contributes a negligible amount of H+ we can also neglect the third step ([H+]HPO4-) or any other consecutive steps. Therefore, only the first equilibrium contributes to the H+ concentration.

Example Find the pH of a 0.10 M H2SO4 (ka2 = 1.7*10-2) Solution The first dissociation is 100% complete, therefore, we have: [H+] = [HSO4-] = 0.10 M from first dissociation. The second dissociation is as follows: HSO4- D H+ + SO42-

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1.7*10-2 = x(0.10 + x)/(0.10 x) assume that 0.10 >> x x = 1.7*10-2 Relative Error = (1.7x10-2/0.10) * 100% = 17% Therefore, the assumption is invalid and the equation must be solved by the quadratic equation.

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Solution H3PO4 D H+ + H2PO4H2PO4- D H+ + HPO42HPO42- D H+ + PO43ka1 = 1.1 x 10-2 ka2 = 7.5 x 10-8 ka3 = 4.8 x 10-13

Since ka1 >> ka2 (ka1/ka2 > 104) the amount of H+ from the second and consecutive equilibria is negligible if compared to that coming from the first equilibrium.

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Therefore, we can say that we only have: H3PO4 D H+ + H2PO4ka1 = 1.1 x 10-2

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Ka1 = x * x/(0.10 x) Assume 0.10>>x since ka1 is small (!!!) 1.1*10-2 = x2/0.10 x = 0.033 Relative error = (0.033/0.10) x 100 = 33% The assumption is invalid and thus we have to use the quadratic equation. If we solve the quadratic equation we get: X = 0.028 Therefore, [H+] = 0.028 M pH = 1.55

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Example Find the pH of a 0.10 M H2CO3 solution. Ka1 = 4.3x10-7, ka2 = 4.8x10-11

Solution We have the following equilibria H2CO3 D H+ + HCO3ka1 = 4.3 x 10-7 HCO3- D H+ + CO32ka2 = 4.8 x 10-11 Since ka1 is much greater than ka2, we can neglect the H+ from the second step

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H2CO3 D H+ + HCO3-

Ka1 = x * x/(0.10 x) Assume 0.10>>x since ka1 is small 4.3*10-7= x2/0.10 x = 2.1x10-4 Relative error = (2.1x10-4/0.10) x 100 = 0.21% The assumption is valid and [H+] = 2.1x10-4 M pH = 3.68

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If we would like to calculate the amount of H+ coming from the second equilibrium ([H+]second step = [CO32-]) we substitute 2.1x10-4 for [H+] as follows:

Ka2 = [H+][CO32-]/[HCO3-]

But from the first step we have [H+] = [HCO3-] ka2 = [CO32-] = 4.8x10-11 = [H+]second step

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Therefore we are justified to omit second dissociation where the hydrogen ion concentration obtained from the first step (2.1x10-4 M) is much greater than the [H+] obtained from the second dissociation (4.8x10-11 M).

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