pH indicators---how they work!

pH indicators are either weak acids or weak bases---that are different in color (change in absorbance) in protonated vs. unprotonated form! They are used at very low concentrations ----to indicate the pH of the solution----with the pH generally being controlled by other components!!

Equilibrium for indicator species: Hin <------> H+ + InKHIn [ H + ][ In ] = [HIn ] [ In ] + log [HIn]

pH = pK HIn

for bromocrescol green----In- is blue and HIn is yellow! at pH 4.7 (the pKa) ---have half in blue form, and half in yellow formget a green color!! Typically---when [Hin]/[In-] > 10 ; color of solution will be color of Hin species; when [In-] / [Hin] > 10 ; color of solution will be color of In- species! By using very low concentrations of indicator---we can get very sharp change in color at equivalence points in pH titrations!

Example of indicator that is diprotic---two different pKa values three different species possible--with three different colors!

at pH << 0.7---solution will be red from pH approx. 0.;7 -2.7; solution will look orange from pH 2.7 --7.9; solution will be yellow from pH 7.9 - 9.9 ; solution will be green at pHs > 9.9; solution will be blue!

Acid-Base Titrations---predicting shape and pH at given points along a titration curve! Different types --a) titration of strong acid with strong base or vica versa! b) titration of weak acid with strong base c) titration of weak base with strong acid Lets start with strong acid/strong base situation-we know that H+ + OH- ------> H2O K = 1/Kw = 1014 ---very favorable reaction---rxn goes to completion! So if we start with base in solution---and add acid---for every proton we add---it will react with hydroxide ion to form water---until there are no more excess hydroxide ions available-equiv. point = pH 7.0 3-regions in titration curve-- 1) before equiv. point; 2) at equiv. point; 3) after equiv. point!

titration of 50 mL of 0.02 M KOH with 0.1 M HBr--need 1 mmole of HBr to neutralize all the base (50 mL x 0.02 = 1 mmole) therefore at equiv. point-MHBr x VHBr = 1 mmole 0.1 x VHBr = 1 mmole VHBr = Ve = 10 mL Lets see what pH is at various points---via calculations---

when no acid added: 0.02 M KOH only present; [OH-] = 0.02 M ; [H+] = 10-14 / 0.02 = 5 x 10-13 M pH = -log [H+] = 12.30 when 3 mL of titrant added: 3 ml x 0.1 M = 0.3 mmoles of acid---means that you decrease total amount of OH- by 0.3 mmoles--therefore: (1.0 mmole - 0.3 mmoles) = 0.7 mmoles OH- still present in solution---but now the total volume = 50 + 3 =53 mL [OH-] = 0.7 / 53 = 0.013 M ; [H+] = 10-14 / 0.013 = 7.69 x 10-13 pH = -log 7.69 x 10-13 = 12.11 when 9.90 mL of acid added: 9.90 x 0.1 M = 0.99 mmoles of acid; thus OH- left = 1.0 - 0.99 = 0.01 mmoles

[OH-] = 0.01/ 59.9 mL = 1.67 x 10-4 [H+] = 10-14/ 1.67 x 10-4 = 5.99 x 10-11 ; therefore pH = 10.22 when 10.0 mL of acid added (equivalence point): 10 mL x 0.1 M = 1.0 mmoles-; no more OH- from the base is present at this point---only OH- is from autoprotolysis of water!-[OH-] = 10-7 ; [H+] = 10-7 ; pH = 7.00 when 10.1 mL of acid added---just beyond equiv. point: 10.1 mL x 0.1 M = 1.01 mmoles; excess H+ by 0.01 mmoles [H+] = 0.01 mmole / 60.1 mL = 1.66 x 10-4 M therefore: pH = -log (1.66 x 10-4) = 3.78 when 11 mL of acid added---far beyond equiv. point: 11 mL x 0.1 M = 1.1 mmoles; excess H+ by 0.1 mmoles [H+] = 0.1 mmole /61.0 mL = 1.64 x 10-3 M pH = -log(1.64 x 10-3) = 2.79

For titration of strong acid with base--the same exact approach is taken to find the pH at various points along the titration curve! Sample problem: Find the pH when 12.75 mL of 0.0501 M NaOH have been added to 25.00 mL of 0.0506 M HClO4 ! how many moles of HClO4 originally present? 25 mL x 0.0506 M = 1.265 mmoles after 12.75 mL base--how many moles of base? 12.75 mL x 0.0501 M = 0.639 mmoles of base---so there must be excess acid still left! How much acid left? 1.265 - 0.639 = 0.626 mmoles What pH? ; [H+] = 0.626 mmoles / 37.75 mL = 0.0166 M pH = -log (0.0166) = 1.78 total volume Find pH after 50 mL of base added?--50 mL x 0.0501 M = 2.505 mmole now have excess base- : 2.505 - 1.265 = 1.24 mmoles NaOH excess [OH-] = 1.24 mmoles / 75 mL = 0.0165 M ; [H+ ] = 10-14 /0.0165 = [H+] = 6.06 x 10-13 ; pH = 12.22

Titration of weak acid with strong base: HA + OH- ------> H2O + AK? = 1/Kb for A-

lets say pKa of HA = 6.15; Ka = 7.08 x 10-7 What is Kb for A- ? recall---Kb = 10-14 / Ka(HA) then Kb = 1.41 x 10-8 ----for rxn in opposite in direction of abovetherefore K = 1/(1.41 x 10-8) = 7.1 x 107 since K is large---neutralization reaction goes completely to right Lets say we have 50.00 mL of 0.0200 M of HA to start in solution! how much volume of 0.1000 M NaOH is needed to reach equiv. point? 50.00 mL x 0.0200 M = 1 mmole of acid present---need 1 mmole of base to reach equivalence point--Therefore--- 0.1000 M x Vbase = 1 mmole; Vbase = 10 mL

Titration of weak acid with strong base: HA + OH- ------> H2O + AK? = 1/Kb for A-

lets say pKa of HA = 6.15; Ka = 7.08 x 10-7 What is Kb for A- ? recall---Kb = 10-14 / Ka(HA) then Kb = 1.41 x 10-8 ----for rxn in opposite in direction of abovetherefore K = 1/(1.41 x 10-8) = 7.1 x 107 since K is large---neutralization reaction goes completely to right Lets say we have 50.00 mL of 0.0200 M of HA to start in solution! how much volume of 0.1000 M NaOH is needed to reach equiv. point? 50.00 mL x 0.0200 M = 1 mmole of acid present---need 1 mmole of base to reach equivalence point--Therefore--- 0.1000 M x Vbase = 1 mmole; Vbase = 10 mL

four regions of the titration curve---1) no base added; what is starting pH? Calculate like weak acid problem- for F= 0.0200 M with Ka = 7.08 x 10-7 x2 / (0.0200 -x) = 7.08 x 10-7 ; x = 1.19 x 10-4 = [H+] ; pH = 3.93 2) initial addition of base to titrate weak acid---becomes buffer system calculation problem----some of HA + OH- -----> A- + H2O For example---say 2 mL of 0.1000 M NaOH--produce 2 mL x 0.1000 M = 0.2 mmoles of Astarting HA = 1 mmole ; therefore after 2 mL of NaOH solution possesses 1.000 - 0.200 = 0.800 mmoles HA and 0.2 mmoles ACan use HH eqn to calculate pH in this region of titration curve-pH = pKa + log ([A-] / [HA]) = 6.15 + log (0.2 / 0.8) = 5.55 note: dont need to calculate conc. of A- and HA--only need mmoles for numerator and demoninator!

when you have added 5 mL of titrant ---then Vbase = 1/2 Veq Exactly 1/2 of the HA has been titrated---This means that [HA] = [A-] ~= 1/2 F --the initial conc. of HA Special situation---since pH = pKa + log ([A-] / [HA]) ---but log term -----> 0 since [HA] = [A-] ; pH = pKa = 6.15 3. At equivalence point (10 mL of NaOH added): All the HA ------> A- and water----Hence the pH at equiv. point is a weak base problem-----A- + H2O <-----> HA + OHmust calculate [OH-] using Kb value--But-- initial F concentration of A- is less than initial [HA] due to dilution by titrant volume! [A-]eq = 1 mmole / 60 mL = 0.01667 M = F (new formal conc.) initial moles of HA at start of titration! total vol. at equiv. point!

Kb for A- = 1.41 x 10-8 = x2 / (F - x) ; F = 0.01667 M X = 1.53 x 10-5 = [OH-] ; [H+] = 10-14 / (1.53 x 10-5) = 6.54 x 10-10 pH = -log(6.54 x 10-10) = 9.18 = pH at equiv. point

4) pH when there is excess strong base----; can assume contribution from weak base A- is negligible! e.g. 11 mL of NaOH added; total volume now = 61.00 mL excess base = 1 mL x 0.1000 M = 0.1 mmole; Therefore: 0.1000 / 61.00 = 0.0016 M = [OH-] thus--[H+] = 10-14 / 0.0016 = 6.25 x 10-12 ; pH = 11.20

This is the actual titration curve for 0.02 M HA with pKa = 6.15 with 0.1000 M NaOH ---we calculated several of the points along the way--on the previous pages!!

Titration of weak base with strong acid---Analogous treatment to titration of weak acid with strong base!!

Ka = 5.92 x 10-6 e.g.---25.00 mL of 0.08364 M pyridine titrated with 0.1067 M HCl mmoles pyridine base = 0.08364 x 25.00 = 2.091 mmoles at equiv. point: VHCl x 0.1067 M = 25.00 mL x 0.08364 ; Ve(HCl) = 19.60 mL HCl What is pH after 4.63 mL of acid added: mmoles acid = 4.63 x 0.1067 = 0.4940 mmole of Pyridinium cation; therefore free base left = 2.091 - 0.4940 = 1.597 mmole Pyridine left thus pH = pKa + log ([pyr] /[[Hpyr+]) = 5.23 + log (1.597 / 0.4940) = pH = 5.74

What would be pH at equivalence point? This is weak acid problem---all of the pyridine converted to Hpyr+; -started with 2.091 mmoles pyridine---will have 2.091 mmoles of pyridinium ion at equivalence point! Ka = 5.92 x 10-6 = x2 / (F - x) F = 2.091 mmoles / (25.0 mL + 19.6 mL) = 0.0469 M Hpyr+ x1 = 1.67 x 10-4 ; x2 (second. approx.) = 1.66 x 10-4 = [H+] pH = 3.78

note: pH at equivalence point is quite low--why? ---because pyridine is very weak base!!---if you calculated pH at start of titration what would it be? 1.69 x 10-9 = x2 / (F -x) ; F= 0.08364 x = [OH-] = 1.19 x 10-5 ; [H+] = 8.40 x 10-10 pH = 9.08

Detecting end points!---use of indicators -choose indicator that has pKa near the equivalence point pH of for titration---so that color change occurs in steepest region of titration curve! - always use small amount of indicator---since they are also acids and bases---hence using high concentrations will consume analyte or titrant!

titration of weak base with pKb = 5.00 with (100 mL of 0.0100 M) with 0.0500 M HCl

With indicators--can only see pH change at end point of titration Use pH electrode to monitor pH of solution throughout titration End point/equivalence point can be determined by either first or second derivative method! slope = pH / vol = 1st derivative second deriv =

( pH / V ) V

endpoint = volume at which second deriv. goes to 0 after inflection

blow-up of second derivative plot near equiv. point!

Can model and predict complete titration of weak base with strong acid---or weak acid with strong base! Results in equations that can be put into Excel spread sheet! for weak acid titrated by strong base:
[ H + ] [OH ] A Ca Cb Vb = = + [ H ] [OH ] Ca Va 1+ Cb

where:

Ka [ H ] + Ka
+

= fraction of HA in A- form! for weak base titrated by strong acid:

= fraction of way to equivalence point Cb =conc. of base Ca = conc. of acid Va = volume of acid Vb = volume of base
BH +

[H + ] = + [ H ] + Ka ( BH + )

example calculated curves for titration of acids with strong base-note: as strength of acid decreases---end points are not sharp, and would be difficult to obtain! obtain curves by putting in different pH values in eqn (then can calc. , [], etc.) and finally Vb values for x-axis!