ChE 413: Desalination

Homework 1: Carbonate Species

1- Calculate the phenolphthalein and total alkalinity of the following samples

a) a 50 mL sample required 5.3 mL of N/50 H2SO4 to reach the phenolphthalein end
point, and a total of 15.2 mL to reach the methyl orange end point.
b) a 100 mL sample required 20.2 mL of N/50 H2SO4 to reach the phenolphthalein
end point, and a total of 25.6 mL to reach the methyl orange end point.

2- Determine the carbonate and hydroxyl ions of the following water samples:
Sample Volume (mL) p-alkalinity, Total-Alk,
(ml 0.02 N H2SO4) (ml 0.02 N H2SO4
1 100 3.0 6.0
2 100 1.5 1.5
3 50 0.0 4.5
4 50 2.5 3.5
5 100 2.0 5.8

3- A 100 ml water sample is titrated for alkalinity by using 0.02 N sulfuric acid. To reach
the phenolphthalein end point requires 3.0 ml, and an additional 12.0 ml is added for
methyl orange color change. Calculate the phenolphthalein and total alkalinities. Give
the ionic forms of the alkalinity present.

4- Calculate [H2CO3*], [HCO3-], [CO32-] and the total carbonate, CT, in an open water
system with a pH of 7.3. The atmosphere contains 10-3.5 atm CO2. Consider the
following reactions:
1- Carbon dioxide dissolved in water as carbonic acid:
CO2 + H2O ↔ H2CO3 , with Kco2 = 10-1.47
2- Carbonic acid dissolved into bicarbonate and carbonate ions:
H2CO3 ↔ H+ + HCO3- , with K1 = 10-6.35
HCO3- ↔ H+ + CO3-- , with K2 = 10-10.33

5- A water sample has a total alkalinity of 220 mg/l and has a pH of 7.4. The maximum
amount of calcium ion is found when the solubility product of CaCO3, Ks = [Ca++]
[CO3--] = 4.57x10-9 , is met. For natural water,

− Talk + [ H + ] − k w /[ H + ]
[ HCO ] =
3
1+ 2k 2 /[ H + ]
Talk + [ H + ] − k w /[ H + ]
[CO3− − ] =
2(1 + [ H + ]/ 2k 2 )
kw= [H+] [OH-]
k2= [H ] [CO3--] / [HCO3-] = 4.69x10-11
+

Calculate the maximum amount of calcium ion in mg/l as CaCO3 that could be
contained in a solution at equilibrium at 25 oC.