Alkalinity

Bicarbonate-carbonate
…the measure of the ability of a water to

neutralize an acid.
Most natural waters are buffered as a result of a
carbon dioxide(air)-bicarbonate (limestone –
CaCO3) buffer system.
What is a buffer?
Mixture of an acid (or base) and its conjugate base (or acid)
Think of chemical equilibrium as a see-saw:
CO2 + H2O ↔ H2CO3
H2CO3 ↔ HCO3- + H+
HCO3- ↔ CO32- + H+
CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+ ↔ CO32- + 2 H+

CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+ ↔ CO32- + 2 H+
CO2
CO32-
If you have a big heavy weight at both ends of the equilibrium,

a small addition of acid or base from an outside source can’t
change the pH very much.
Alkalinity can be reported in several ways –
ways which are not completely chemically
accurate.
Alkalinity as mg/L CaCO3

= ml titrant * Normality of acid * 50,000
mL sample
Normality is like Molarity with the
stoichiometry added right in.
Normality (N) = equivalent moles of solute

L
What’s “equivalent” mean? It means you

consider the reaction.
1.5 M HCl
What’s HCl?
It’s an acid. What’s the relevant part of the acid?
H+
HCl + OH-  H2O + Cl-

1.5 M HCl
Since 1 HCl reacts with 1 OH-, there is one chemical
equivalent per molecule.
1.5 mole HCl * 1 H+ equivalent = 1.5 N HCl
L 1 HCl
HCl + OH-  H2O + Cl-

1.5 M H2SO4
What’s H2SO4?
It’s an acid. What’s the relevant part of the acid?
H+
H2SO4 + 2 OH-  2 H2O + SO42-

1.5 M H2SO4
Since 1 H2SO4 reacts with 2 OH-, there are TWO
chemical equivalents per molecule.
1.5 mole H2SO4 * 2 H+ equivalent = 3.0 N H2SO4

L 1 H2SO4
H2SO4 + 2 OH-  2 H2O + SO42-

I titrate 50.00 mL of calcium carbonate solution
using a 1.5 M H2SO4 solution. Equivalence
(2nd endpoint) is reached after addition of
32.65 mL of acid. What is the concentration
of calcium carbonate in the original sample in
mg/L?
1st thing we need?
Balanced Equation
CO32- + 2 H+  H2CO3
OR
CO32- + H+  HCO3-
HCO3- + H+  H2CO3
1.5 moles H2SO4 * 0.03265 L = 0.048975 mol H2SO4
1L
0.048975 mol H2SO4 * 2 mol H+ = 0.09795 mol H+
1 mol H2SO4
0.09795 mol H * 1 mol CO32- = 0.048975 mol CO32-
+
2 mol H+
0.048975 mol CO32- 1 mol CaCO3 = 0.048975 mol CaCO3
1 mol CO32-
0.048975 mol CaCO3* 100.09 g * 1000 mg = 98039 mg/L
0.050 L 1 mol CaCO3 1 g
3 equivalents H2SO4 * 0.03265 L = 0.09795 eq H2SO4
1L
0.09795 eq H2SO4 * = 0.09795 mol H+
0.09795 mol H+ * 1 mol CO32- = 0.048975 mol CO32-

2 mol H+
0.048975 mol CO32- * 100.09 g * 1000 mg = 98039 mg/L

0.050 L 1 mol CO32- 1 g
Alkalinity as mg/L CaCO3
= ml titrant * Normality of acid * 50,000
mL sample
= 32.65 mL * 3.0 N H2SO4 * 50,000
50 mL
=97950 mg/L
The expression in the book (or lab) is just the

Moles! Moles! Moles! solved for you.
If you titrate a solution with multiple bases, can you
tell what reacts with what?
Essentially, you have 3 different bases in the system:
OH-, CO32-, and HCO3-
All 3 can be neutralized by addition of a strong acid.
H+ + OH-  H2O (neutral)
H+ + CO32-  HCO3-
HCO3- + H+  H2CO3
(slightly basic) (acidic)
HCO3- + H+  H2CO3
(acidic)
H+ + OH-  H2O (neutral – EP1)
H+ + CO32-  HCO3-
HCO3- + H+  H2CO3
(slightly basic – EP1) (acidic – EP2)
HCO3- + H+  H2CO3
(acidic – EP2)
OH- is a strong base.
HCO3- is a weak acid
If I have more OH- than HCO3-, it completely

neutralizes it and I just have OH-
If I have more HCO3- than OH-, then it partially
neutralizes it and I detect only HCO3-
I titrate a 25.00 mL water sample with 0.1250 M
HCl. I achieve the first endpoint at 22.5 mL of
HCl and the second after addition of another
27.6 mL of HCl.
What can I conclude?

Possible EP1 vol EP2 vol Compare
CO32- X X EP1 = EP2
HCO3- 0 Y EP1 = 0
OH- z 0 EP2 =0
CO32- x (x+y) EP1<EP2

HCO3- EP1 not 0
CO32- (x+z) X EP1>EP2
OH- EP2 not 0
HCO3- ??? ???? ????
OH-
I titrate a 25.00 mL water sample with 0.1250 M HCl. I achieve
the first endpoint at 22.5 mL of HCl and the second after
addition of another 27.6 mL of HCl.
Carbonate and bicarbonate are both present.
How much?
0.1250 M HCl * 0.0225 L HCl = 2.813x10-3 mol HCl
2.813x10-3 moles CO32-
0.1250 M HCl * (0.0276 – 0.0225 L HCl) = 6.375x10-4 H+
6.375x10-4 moles HCO3-
Carbonate and bicarbonate are usually measured as “mg equivalent CaCO3/L”
So…
0.1250 M HCl * 0.0225 L HCl = 2.813x10-3 mole H+
2.813x10-3 mole H+ * 1 mol CO32-
1 mol H+ =2.813x10-3 moles CO32-
2.813x10-3 moles CO32- * 1 mol CaCO3
1 mol CO32-
2.813x10-3 mol CaCO3*100.08 g = 0.2815 g
mol CaCO3
0.2815 g CaCO3 * 1000 mg = 281.5 mg CaCO3
1g
281.5 mg CaCO3 = 11,259 mg CaCO3/L
0.025 L
CO32- + 2 H+ = H2CO3
HCO3- + H+ = H2CO3
0.1250 M HCl * (0.0276 – 0.0225 L HCl) = 6.375x10-4 moles HCl 6.375x10-4

moles HCl * 1 mol CO3-2 = 3.1875x10-4 moles CO32-
2 mol H+
3.1875x10-4 moles CO32- *100.08 g = 0.031901 g
mol CaCO3
0.031901 g CaCO3 * 1000 mg = 31.90 mg CaCO3
1g
31.90 mg CaCO3 = 1276.0 mg CaCO3/L
0.025 L
I titrate a 25.00 mL water sample with 0.1250 M HCl. I achieve the first
endpoint at 22.5 mL of HCl and the second after addition of another 27.6
mL of HCl. What is the total alkalinity?
Assume the second endpoint is reached and it was all CaCO3 in the sample.
22.5 mL + 27.6 mL = 50.1 mL total HCl
0.1250 M HCl * 0.0501 L = 6.2625x10-3 mol HCl
6.2625x10-3 mol H+ *1 mol CaCO3 * 100.08 g * 1000 mg=313.38 mg CaCO3
2 mol HCl mol 1g
313.38 mg CaCO3 = 12,535 mg CaCO3/L

0.025 L
Total alkalinity = 12,535 mg CaCO3/L
Carbonate alkalinity = 11, 260 mg CaCO3/L
Bicarbonate alkalinity = 1276 mg/L
11,260 + 1276 = 12536 mg CaCO3/L!!!!

I titrate a water sample with 0.1250 M HCl. I achieve
the first endpoint at 22.5 mL of HCl and the second
after addition of another 27.6 mL of HCl.

Is this really true?

I titrate a water sample with 0.1250 M HCl. I achieve
the first endpoint at 22.5 mL of HCl and the second
after addition of another 27.6 mL of HCl.
Is this really true?
No – any chemical species that behaves like carbonate
or like bicarbonate will look identical!!!!!!!
I titrate a 50.00 mL water sample with 0.1250 M HCl. I
achieve the first endpoint at 22.5 mL of HCl and the
second after addition of another 19.6 mL of HCl.
What is the total alkalinity in mg CaCO3/L?
What can I conclude about the species present?

Possible EP1 vol EP2 vol Compare
CO32- X X EP1 = EP2
HCO3- 0 Y EP1 = 0
OH- z 0 EP2 =0
CO32- x (x+y) EP1<EP2

HCO3- EP1 not 0
CO32- (x+z) X EP1>EP2
OH- EP2 not 0
HCO3- ??? ???? ????
OH-
I titrate a 50.00 mL water sample with 0.1250 M HCl. I
achieve the first endpoint at 22.5 mL of HCl and the
second after addition of another 19.6 mL of HCl.
What is the total alkalinity in mg CaCO3/L?

Carbonate and OH- are both present.
BUT if I only care about total alkalinity I just ASSUME
it is all CaCO3!!!!
22.5 mL + 19.6 mL = 42.1 mL
0.1250 M * 0.0421 L = 5.2625x10-3 mol H+
5.2625x10-3 mol H+ * 1 mol CaCO3 = 2.6313x10-3 mol CaCO3
2 mol H+
2.6313x10-3 mol * 100.08 g * 1000 mg = 263.34 mg CaCO3
mol CaCO3 1 g
263.34 mg CaCO3 = 5267 mg CaCO3/L
0.050 L

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Bicarbonate-carbonate

…the measure of the ability of a water to

CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+ ↔ CO32- + 2 H+

If you have a big heavy weight at both ends of the equilibrium,

Alkalinity as mg/L CaCO3

Normality (N) = equivalent moles of solute

What’s “equivalent” mean? It means you

It’s an acid. What’s the relevant part of the acid?

HCl + OH-  H2O + Cl-

HCl + OH-  H2O + Cl-

It’s an acid. What’s the relevant part of the acid?

H2SO4 + 2 OH-  2 H2O + SO42-

1.5 mole H2SO4 * 2 H+ equivalent = 3.0 N H2SO4

H2SO4 + 2 OH-  2 H2O + SO42-

0.09795 eq H2SO4 * = 0.09795 mol H+

0.09795 mol H+ * 1 mol CO32- = 0.048975 mol CO32-

0.048975 mol CO32- * 100.09 g * 1000 mg = 98039 mg/L

The expression in the book (or lab) is just the

HCO3- is a weak acid

If I have more OH- than HCO3-, it completely

What can I conclude?

CO32- X X EP1 = EP2

CO32- x (x+y) EP1<EP2

0.1250 M HCl * (0.0276 – 0.0225 L HCl) = 6.375x10-4 moles HCl 6.375x10-4

313.38 mg CaCO3 = 12,535 mg CaCO3/L

Carbonate alkalinity = 11, 260 mg CaCO3/L

Bicarbonate alkalinity = 1276 mg/L

11,260 + 1276 = 12536 mg CaCO3/L!!!!

What can I conclude?

Is this really true?

What can I conclude about the species present?

CO32- X X EP1 = EP2

CO32- x (x+y) EP1<EP2

What can I conclude?

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