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Chapter 15: Applications of Aqueous Equilibria. AP Chemsitry. Titrations and pH Curves. How does the pH of 50.0 ml 0.100 M HCl change as 0.200 M NaOH is added? STRONG ACID—STRONG BASE pH before any NaOH is added? major species? HCl H + + Cl - [0.100 M] [0.100 M] [0.100 M].
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Chapter 15: Applications of Aqueous Equilibria AP Chemsitry
Titrations and pH Curves How does the pH of 50.0 ml 0.100 M HCl change as 0.200 M NaOH is added? STRONG ACID—STRONG BASE • pH before any NaOH is added? major species? HCl H+ + Cl- [0.100 M] [0.100 M] [0.100 M] H+ Cl- H2O pH = -log (0.100) = 1.000
50.0 ml 0.100 M HCl 10.0 ml 0.200 M NaOH 2.pH after some NaOH is added • Add 10.0 ml 0.200 M NaOH major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(60) MT = 0.0833 M For OH- (0.2)(10) = MT(60) MT = 0.0333 M 60.0 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.08330.0333 --- 0.0333 0.0333 --- 0.0500≈0 --- major species? H+ H2O pH = -log (0.0500) = 1.300
50.0 ml 0.100 M HCl 20.0 ml 0.200 M NaOH pH after some NaOH is added ii. Add 20.0 ml 0.200 M NaOH major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(70) MT = 0.0714 M For OH- (0.2)(20) = MT(70) MT = 0.0571 M 70.0 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.07140.0571 --- 0.0571 0.0571 --- 0.0143≈0 --- major species? H+ H2O pH = -log (0.00143) = 1.845
50.0 ml 0.100 M HCl 24.0 ml 0.200 M NaOH pH after some NaOH is added iii. Add 24.0 ml 0.200 M NaOH major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(74) MT = 0.0676 M For OH- (0.2)(25) = MT(74) MT = 0.0649 M 74.0 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.06760.0649 --- 0.0649 0.0649 --- 0.0027≈0 --- major species? H+ H2O pH = -log (0.0027) = 2.569
50.0 ml 0.100 M HCl 24.9 ml 0.200 M NaOH pH after some NaOH is added iv. Add 24.9 ml 0.200 M NaOH major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(74.9) MT = 0.0668 M For OH- (0.2)(25) = MT(74.9) MT = 0.0665 M 74.9 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.06680.0665 --- 0.0665 0.0665 --- 0.0003≈0 --- major species? H+ H2O pH = -log (0.0003) = 3.523
50.0 ml 0.100 M HCl 25.0 ml 0.200 M NaOH pH after some NaOH is added vi. Add 25.0 ml 0.200 M NaOH major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(75) MT = 0.0667 M For OH- (0.2)(25) = MT(75) MT = 0.0667 M 75.0 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.06670.0667 --- 0.0667 0.0667 --- ≈0≈0 --- major species? H2O pH = -log(1 X 10-7) = 7
equivalence point (mol H+ = mol OH-)
50.0 ml 0.100 M HCl 30.0 ml 0.200 M NaOH 3. pH after 30 ml NaOH added major species? H+ Cl- Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(80) MT = 0.0625 M For OH- (0.2)(25) = MT(80) MT = 0.075 M 80.0 ml total
Step 2: Neutralization Banana Chart: Before, Neutralization, After H+ + OH- H2O B N A 0.06250.0750 --- 0.0625 0.0625 --- ≈00.0125 --- major species? OH- H2O pOH = -log (0.0125) = 1.903 pH = 14 – pOH = 14 – 1.903 = 12.097
Figure 15.1The pH Curve for the Titration of 50.0 mL of 0.200 M HNO3 with 0.100 M NaOH
WEAK ACID—STRONG BASE How does the pH of 50.0 ml 0.100 M acetic acid sol’n change as 0.200 M NaOH is added? • pH before any NaOH is added? major species? HC2H3O2 H2O
ICE, ICE, BABY Eqn? HC2H3O2 H+ + C2H3O2- I C E 0.100 ≈0 ≈0 -x +x +x 0.100-x x x
HC2H3O2 H+ + C2H3O2- I C E 0.100 ≈0 ≈0 -0.00134 +0.00134 +0.00134 ≈ 0.100 0.00134 0.00134 x = 0.00134 pH = -log (0.00134) = 2.872
50.0 ml 0.100 M HAc 5.0 ml 0.200 M NaOH 2.pH after some NaOH is added • Add 5.0 ml 0.200 M NaOH major species? HC2H3O2 Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(55) MT = 0.0909 M For OH- (0.2)(5) = MT(55) MT = 0.0182 M 55.0 ml total
Step 2: Neutralization HC2H3O2 OH- H2O major species: Eqn? HC2H3O2 + OH- H2O + C2H3O2- B N A 0.09090.0182 --- ≈0 0.0182 0.0182 --- 0.0182 0.0727≈0 --- 0.0182 major species? HC2H3O2 C2H3O2- H2O Eqn? HC2H3O2 H+ + C2H3O2-
ICE, ICE, BABY HC2H3O2 H+ + C2H3O2- I C E 0.0727 ≈0 0.0182 -x +x +x 0.0727-x x 0.0182+x x = 7.19 X 10-5
HC2H3O2 H+ + C2H3O2- I C E 0.0727 ≈0 0.0182 7.19 X 10-5 +7.19 X 10-5 + 7.19 X 10-5 ≈0.0727 7.19 X 10-5≈0.0182 pH = -log (7.19 X 10-5) = 4.143
Terms: Common Ion Effect: HC2H3O2 H+ + C2H3O2- Add NaC2H3O2? A response to the addition of an ion already involved in the equilibrium
Buffered Solution: A sol’n that RESISTS a change in the pH Made up of: A WEAK ACID and its SALT OR A WEAK BASE and its SALT i.e. HA and NaA i.e. B and BHCl NH3 and NH4Cl
Why WEAK acids and bases? do not 100% dissociate HA + H2O H3O+ + A- add H+? Shift makes more acid (HA) add OH-? Shift makes more base (A-) Acid Base C.Acid C. Base
Why WEAK acids and bases? do not 100% dissociate B + H2O BH+ + OH- add H+? Shift makes more acid (BH+) add OH-? Shift makes more base (B) Acid Base C.Acid C. Base
50.0 ml 0.100 M HAc 10.0 ml 0.200 M NaOH 2.pH after some NaOH is added ii. Add 10.0 ml 0.200 M NaOH major species? HC2H3O2 Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(60) MT = 0.0833 M For OH- (0.2)(10) = MT(60) MT = 0.0333 M 60.0 ml total
HC2H3O2 H+ + C2H3O2- Step 2: Neutralization HC2H3O2 OH- H2O major species: Eqn? HC2H3O2 + OH- H2O + C2H3O2- B N A 0.08330.0333 --- ≈0 0.0333 0.0333 --- 0.0333 0.0500≈0 --- 0.0333 major species? HC2H3O3 C2H3O2- H2O Eqn?
ICE, ICE, BABY Or……….. Henderson-Hasselbalch Eqn
ICE, ICE, BABY HC2H3O2 H+ + C2H3O2- I C E 0.0500 ≈0 0.0333 -x +x +x 0.05-x x 0.0333+x x = 2.70 X 10-5
HC2H3O2 H+ + C2H3O2- I C E 0.0500 ≈0 0.0333 2.70 X 10-5 +2.70 X 10-5 +2.70 X 10-5 ≈0.0500 2.70 X 10-5≈0.0333 pH = -log (2.70 X 10-5) = 4.568
Or…H-H Eqn 4.74
50.0 ml 0.100 M HAc 12.5 ml 0.200 M NaOH 2.pH after some NaOH is added iii. Add 12.5 ml 0.200 M NaOH major species? HC2H3O2 Na+ OH- H2O MoVo = MTVT Step 1: DILUTION For H+ (0.1)(50) = MT(62.5) MT = 0.0800 M For OH- (0.2)(12.5) = MT(62.5) MT = 0.0400 M 62.5 ml total
HC2H3O2 H+ + C2H3O2- Step 2: Neutralization HC2H3O2 OH- H2O major species: Eqn? HC2H3O2 + OH- H2O + C2H3O2- B N A 0.08000.0400 --- ≈0 0.0400 0.0400 --- 0.0400 0.0400≈0 --- 0.0400 major species? HC2H3O3 C2H3O2- H2O Eqn?
ICE, ICE, BABY Or……….. Henderson-Hasselbalch Eqn
ICE, ICE, BABY HC2H3O2 H+ + C2H3O2- I C E 0.0400 ≈0 0.0400 -x +x +x 0.04-x x 0.04+x x =1.80 X 10-5
HC2H3O2 H+ + C2H3O2- I C E 0.0400 ≈0 0.0400 1.80 X 10-5 +1.80 X 10-5 +1.80 X 10-5 ≈0.0400 1.80 X 10-5≈0.0400 pH = -log (1.80 X 10-5) = 4.745
Or…H-H Eqn 4.74 =1!!!