Excelet

Exploring Acid-Base Titration Curves

What does a graph of pH as a function of titrant volume look like?

How does the graph responds to the acid's strength, K a?

What do the derivatives of the titration curve look like?

titrant?

derivative? pH

Click on the tabs to navigate!!!

volume of titrant
Acid-Base Chemistry for a Titration Curve

Here we consider a monoprotic acid being neutralized by NaOH, always the titrant used here.

HA + NaOH -----> NaA + H20

The acid, HA, may be a strong acid or a weak acid, where we can vary the acid strength or K a.

The equivalence point or point of complete neutralization of the reaction:

moles acid = moles base

The equivalence point pH is controlled by the behavior of the salt, NaA, formed in the neutralization.

Since moles = M x VL, we can find the concentration of an unknown acid, evaluate its K a, and find its molar mass.

Objective:
In this excelet, we will examine the behavior of titration curves, their derivatives for finding the
equivalence point, tracking the reaction progress for composition, and selecting an indicator.

Sinex 2011
Comparing Titration Curves
plot the first derivatives
Acid 1 turn curve0on/off Acid 2 ✘ turn curve1on/off 0
✘ First Derivative

acid, mmol 2.5 (CHA) 2.5 (CHA2)

titrant, M 0.1 (COH) 0.1 (COH2) ✘ 1 line
pH = 7 reference First Derivative1
total volume, mL 50 V_o 50 V_o2
pKa 4 -2 strong acid
adjust strength 7 0
The first derivative is a
14 reference 1 plot of DpH/DV as a function
13 0 7 0.9
of the average volume of the
12 50 7 two points to get the slope.
11 0.8

derivative
10 line showing slope 0.7 slope = DpH/DV
9 vol pH
0.6
pH 8 -50000 -2 slope = 2
7 -50000 -2 0.5
6 This will show a green line
0.4
5
on the BLUE titration curve
4 0.3
ONLY.
3 0.2 Use the spinner to adjust!
2
0.1
1
0 0
0 5 10 15 Volume20of Titrant,
25 mL NaOH
30 35 40 45 50

Sinex 2011

V pH alpha Vave DpH/DV V pH alpha Vave DpH/D

1 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! -475.2475 0 0.009901 -304.2201 0.001462
2 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! -133.1927 0.5 0.003152 -79.10883 0.004622
3 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! -25.02498 1 0.000999 -7.922133 0.014617
4 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 9.180709 1.5 0.000316 14.5891 0.046224
5 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 19.9975 2 1E-04 21.70779 0.146174
6 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 23.41807 2.5 3.162E-05 23.95891 0.462244
7 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.49975 3 1E-05 24.67078 1.461744
8 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.84181 3.5 3.162E-06 24.89589 4.62244
9 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.94998 4 1E-06 24.96708 14.6174
10 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.98418 4.5 3.162E-07 24.98959 46.22296
11 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.995 5 1E-07 24.99671 146.1283
12 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.99842 5.5 3.162E-08 24.99896 460.7878
13 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.9995 6 1E-08 24.99968 1416.959
14 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 24.99986 6.5 3.162E-09 24.99993 3512.308
15 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25 7 1E-09 25.00007 3513.22
16 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.00014 7.5 3.162E-10 25.00032 1417.624
17 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.00049 8 1E-10 25.00104 461.0167
18 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.00158 8.5 3.162E-11 25.00329 146.2013
19 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.005 9 1E-11 25.01041 46.24607
20 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.01581 9.5 3.162E-12 25.03291 14.62471
21 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.05 10 1E-12 25.10406 4.624751
22 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.15811 10.5 3.162E-13 25.32906 1.462475
23 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 25.5 11 1E-13 26.04057 0.462475
24 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 26.58114 11.5 3.162E-14 28.29057 0.146248
25 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 30 12 1E-14 35.40569 0.046248
26 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 40.81139 12.5 3.162E-15 57.90569 0.014625
27 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 75 13 1E-15 129.0569 0.004625
28 -50000 -2 0.999999 -50000 #DIV/0! #DIV/0! 183.1139 13.5 3.162E-16 354.0569 0.001462
29 -50000 -2 0.999999 525 14 1E-16

pH
 0
0.5 Excel for chemists: a comprehensive guide,
1 By E. Joseph Billo (1997)
1.5
2
2.5 Simulation of Titration Curves
3 Using a Single Master Equation
3.5 Ch. 20, pp.337-338
4
4.5
5
5.5
6
6.5
7
7.5
8
8.5
9
9.5
10
10.5
11
11.5
12
12.5
13
13.5
14
DpH/DV
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
-10
Comparing the Derivatives of a Titration Curve
plot the derivatives
Acid 0
First Derivative
weak acid, mmol 2.5
titrant, M 0.1 0 line
pH = 7 reference 0
Second Derivative
total volume, mL 50
pKa 5
adjust strength 7 Adjust the scaling factor to
help view the derivatives!
14 12 scaling factor
13 0 -2 2
12 50 -2 10
11

derivative
10
8
9
The derivative scale
pH 8
on the right side of the graph
7 6
will rescale for the derivatives
6
(note the zero mores!).
5
4
4
3
2
2
1
0 0
0 5 10 15 Volume
20of Titrant,
25 mL NaOH
30 35 40 45 50

Sinex 2011

V pH alpha Vave DpH/DV Vave D(DpH/DV)/DVave

 -500 0 0.99999 -329.0564 -10 0.001462 -216.5559 -10 1.405E-05 1.405E-07
-158.1131 0.5 0.999968 -104.0553 -10 0.004625 -68.47789 -10 0.000141 1.405E-06
-49.9975 1 0.9999 -32.90049 -10 0.014622 -21.64487 -10 0.001402 1.402E-05
-15.80349 1.5 0.999684 -10.38926 -10 0.046175 -6.813967 -10 0.013678 0.000137
-4.975025 2 0.999001 -3.238678 -10 0.14398 -2.058041 -10 0.108444 0.001084
-1.502331 2.5 0.996848 -0.877403 -10 0.400046 -0.349765 -10 0.171404 0.001714
-0.252475 3 0.990099 0.177873 -10 0.580924 0.796674 -10 -0.21916 -0.002192
0.608222 3.5 0.969347 1.415475 -10 0.309692 2.761048 -10 -0.065767 -0.000658
2.222727 4 0.909091 4.106621 -10 0.132704 6.6746898 -10 -0.010871 -0.000109
5.990516 4.5 0.759747 9.242758 -10 0.07687 12.493153 -10 1.345E-05 1.345E-07
12.495 5 0.5 15.74355 -10 0.076957 18.301491 -10 0.011127 0.000111
18.99209 5.5 0.240253 20.85944 -10 0.13388 22.169793 -10 0.075537 0.000755
22.72678 6 0.090909 23.48015 -10 0.331841 23.986574 -10 0.623624 0.006236
24.23352 6.5 0.030653 24.493 -10 0.963478 24.664952 -10 5.808462 0.058085
24.75248 7 0.009901 24.8369 -10 2.961045 24.892666 -10 56.19082 0.561908
24.92133 7.5 0.003152 24.94843 -10 9.227578 24.966513 -10 506.2341 5.062341
24.97552 8 0.000999 24.9846 -10 27.53852 24.991343 -10 2159.326 21.59326
24.99368 8.5 0.000316 24.99809 -10 56.66758 25.003424 -10 -1568.048 -15.68048
25.0025 9 1E-04 25.00876 -10 39.93312 25.020573 -10 -1080.886 -10.80886
25.01502 9.5 3.162E-05 25.03239 -10 14.39708 25.068139 -10 -136.7645 -1.367645
25.04975 10 1E-05 25.10389 -10 4.617451 25.216449 -10 -14.01613 -0.140161
25.15803 10.5 3.162E-06 25.329 -10 1.462244 25.684779 -10 -1.405072 -0.014051
25.49997 11 1E-06 26.04055 -10 0.462468 27.165559 -10 -0.140542 -0.001405
26.58113 11.5 3.162E-07 28.29056 -10 0.146247 31.848128 -10 -0.014055 -0.000141
30 12 1E-07 35.40569 -10 0.046248 46.655693 -10 -0.001405 -1.41E-05
40.81139 12.5 3.162E-08 57.90569 -10 0.014625 93.481317 -10 -0.000141 -1.41E-06
75 13 1E-08 129.0569 -10 0.004625 241.55694 -10 -1.41E-05 -1.41E-07
183.1139 13.5 3.162E-09 354.0569 -10 0.001462
525 14 1E-09
Excel for chemists: a comprehensive guide,
By E. Joseph Billo (1997)

Simulation of Titration Curves

Using a Single Master Equation
Ch. 20, pp.337-338
Tracking the Reaction Progress
HA + NaOH -----> NaA + H20 What is the composition of the
Acid flask as the titration proceeds?
weak acid, mmol 2.5 (HA)o = 0.025 M
titrant, M 0.1 0 line
pH = 7 reference
total volume, mL 100
pKa 4 The inset composition graph will respond
adjust strength 6 as the red trace point is moved. Control of the Tracer Point
volume of
14 reference line titrant pH
13 0 -2 2.66
12 30 -2 2660
11 bar graph composition increase the volume to track
10
HA 0.023907

c o n c en tratio n
9
A- 0.001093 (A-)/(HA) =
pH 8
Na+ -0.00219 0.03
7
0.025
6
0.02
5
0.015
4
0.01
3
0.005
2
0
1 HA A- Na+
0
0 5 10 15 20 of Titrant,
Volume 25 mL NaOH
30 35 40 45 50

Sinex 2011

V pH alpha HA alpha A- (A-)/(HA)

-999.9975 0 0.9999 1E-04 0.0001
-316.2199 0.5 0.999684 0.000316 0.000316
-99.97502 1 0.999001 0.000999 0.001
-31.54397 1.5 0.996848 0.003152 0.003162
-9.752475 2 0.990099 0.009901 0.01 Excel for chemists: a comprehensive guide,
-2.395942 2.5 0.969347 0.030653 0.031623 By E. Joseph Billo (1997)
1.272727 3 0.909091 0.090909 0.1
5.690099 3.5 0.759747 0.240253 0.316228
12.4 4 0.5 0.5 1 Simulation of Titration Curves
18.96205 4.5 0.240253 0.759747 3.162278 Using a Single Master Equation
22.71727 5 0.090909 0.909091 10 Ch. 20, pp.337-338
24.23051 5.5 0.030653 0.969347 31.62278
24.75149 6 0.009901 0.990099 100
24.92091 6.5 0.003152 0.996848 316.2278 The tracking bar graph idea is from:
24.97502 7 0.000999 0.999001 1000 http://chemlinks.beloit.edu/rain/pages/titr.html
24.99238 7.5 0.000316 0.999684 3162.278 click here
24.99849 8 1E-04 0.9999 10000
25.00237 8.5 3.162E-05 0.999968 31622.78
25.00975 9 1E-05 0.99999 100000
25.03154 9.5 3.162E-06 0.999997 316227.8
25.09997 10 1E-06 0.999999 1000000
25.31622 10.5 3.162E-07 1 3162278
26 11 1E-07 1 10000000
28.16228 11.5 3.162E-08 1 31622777
35 12 1E-08 1 1E+08
56.62278 12.5 3.162E-09 1 3.16E+08
125 13 1E-09 1 1E+09
341.2278 13.5 3.162E-10 1 3.16E+09
1025 14 1E-10 1 1E+10
-1.09499 3 0.956289 0.043711 0.045709 tracer point
me to track
Selecting an Indicator
HA + NaOH -----> NaA + H20 To select an indicator: the
Acid pH equivalence point = pKIn +/- 1
acid, mmol 2.5 (HA)o = 0.25 M
titrant, M 0.1 0 line
pH = 7 reference
total volume, mL 10
pKa -2 strong acid The color change range of an indicator is shown
adjust strength 0 based on pKIn +/- 1, which defines the end point. Control of the Tracer Point
pKIn
14 reference line 8.70
13 0 -2 8699
12 50 -2 adjust the indicator constant
11 bar graph composition
10 HA 5E-12 2 indicator pKIn
9 A- 0.25 methyl yellow 3.1
1 2
pH 8 Na+ 0.050001 bromophenol blue 4.2
2
7 methyl orange 3.5
6 bromocresol green 4.9
5 methyl red 5.0
4 bromocresol purple 6.5
3
bromothymol blue 7.3
2
cresol red 8.4
1
phenol red 8.0
0
thymol blue 9.0
0 5 10 15 20 of Titrant,
Volume 25 mL NaOH
30 35 40 45 50
phenolphthalein 8.7
thymolphthalein 9.2
Sinex 2011

V pH alpha HA alpha A- (A-)/(HA)

-75.24752 0 0.009901 0.990099 100
-6.701584 0.5 0.003152 0.996848 316.2278
14.97502 1 0.000999 0.999001 1000
21.82982 1.5 0.000316 0.999684 3162.278
23.9975 2 1E-04 0.9999 10000 Excel for chemists: a comprehensive guide,
24.68298 2.5 3.162E-05 0.999968 31622.78 By E. Joseph Billo (1997)
24.89975 3 1E-05 0.99999 100000
24.9683 3.5 3.162E-06 0.999997 316227.8
24.98998 4 1E-06 0.999999 1000000 Simulation of Titration Curves
24.99683 4.5 3.162E-07 1 3162278 Using a Single Master Equation
24.999 5 1E-07 1 10000000 Ch. 20, pp.337-338
24.99968 5.5 3.162E-08 1 31622777
24.9999 6 1E-08 1 1E+08
24.99997 6.5 3.162E-09 1 3.16E+08 The indicator color range and error idea is from:
25 7 1E-09 1 1E+09 http://chemlinks.beloit.edu/rain/pages/titr.html
25.00003 7.5 3.162E-10 1 3.16E+09 click here
25.0001 8 1E-10 1 1E+10
25.00032 8.5 3.162E-11 1 3.16E+10
25.001 9 1E-11 1 1E+11 Indicator constants from:
25.00316 9.5 3.162E-12 1 3.16E+11 Flaschka and others (1969) Quantitative Analytical
25.01 10 1E-12 1 1E+12 Chemistry, Volume I
25.03162 10.5 3.162E-13 1 3.16E+12
25.1 11 1E-13 1 1E+13
25.31623 11.5 3.162E-14 1 3.16E+13
26 12 1E-14 1 1E+14
28.16228 12.5 3.162E-15 1 3.16E+14
35 13 1E-15 1 1E+015
56.62278 13.5 3.162E-16 1 3.16E+15
125 14 1E-16 1 1E+016
25.005 9.70 2E-12 1 5E+11 pKin +1
25.0005 8.70 2E-11 1 5E+10 tracer point -pKin
25.00005 7.70 2E-10 1 5E+09 pKin -1

0 10 0 9 0 8
25.005 10 25.0005 9 25.00005 8 indicator range and error
25.005 0 25.0005 0 25.00005 0
Analyzing Titration Curve Data

volume, mL pH volaverage DpH/Dvol The Task:

0 2.51 0.795 0.528302 1. Plot the titration curve data
1.59 3.35 1.925 0.313433
2.26 3.56 2.92 0.143939 2. Calculate the first derivative (see the comment box) and plot it.
3.58 3.75 4.05 0.255319
4.52 3.99 4.75 0.043478 3. Locate the equivalence point. What are its coordinates (vol, pH)?
4.98 4.01 5.115 0.407407
5.25 4.12 5.885 0.15748 4. Find the Ka of the weak acid.
6.52 4.32 7.18 0.098485
7.84 4.45 8.7 0.075581 5. From the indicator tab, select an indicator that will work for
9.56 4.58 9.89 0.272727 this titration.
10.22 4.76 10.73 0.058824
11.24 4.82 11.71 0.095745
12.18 4.91 12.9 0.118056
13.62 5.08 14.07 0.055556
14.52 5.13 14.8 0.196429
15.08 5.24 15.53 0.155556
15.98 5.38 16.09 0.227273
16.2 5.43 17.27 0.074766
18.34 5.59 18.8 0.282609
19.26 5.85 19.45 0.421053
19.64 6.01 19.925 0.859649
20.21 6.5 20.285 2
20.36 6.8 20.45 4.055556
20.54 7.53 20.62 15.3125 Sinex 2011
20.7 9.98 20.755 2.909091
20.81 10.3 20.87 1.666667
20.93 10.5 20.98 1.1
21.03 10.61 21.12 0.611111
 21.21 10.72 21.275 1.230769
21.34 10.88 21.405 0.384615
21.47 10.93 21.615 0.310345
21.76 11.02 22.025 0.301887
22.29 11.18 22.965 0.02963
23.64 11.22 24.045 0.148148
24.45 11.34 25.84 0.071942
27.23 11.54 28.34 0.022523
29.45 11.59 33.125 0.002721
36.8 11.61

data from: chemlabs.uoregon.edu/GeneralResources/pdf/equivPt_text.pdf

Analyzing a Titration Curve

The Task:
What is being titrated? Why?

What is the equivalence point pH? Why?

If the starting pH was 1.30, what is the

molarity of acid?

Would phenolphthalein work as an indicator?

Why or why not?

Sinex 2011