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Chapter 10 Summary
Dr. Rahni
Analytical Chemistry
Method
that interact with one another and water to yield two or more equilibria that
function simultaneously.
above system, there are five species: Ba2+, SO42-, HSO4-, H3O+, and OH-.
i) Equilibrium-constant expressions
Example 10-1
write equations for three equilibria that must be present in this solution.
Because the only source for the two sulfate species is the dissolved
BsSO4, the barium ion concentration must equal the total concentration of
The hydronium ion concentration in this solution has two sources: one
from the HCl and the other from the dissociation of the solvent. A second mass-
Example 10-2
AgBr(s) Ag+ + Br -
Because the only source of Ag+, Br -, and Ag(NH3)2+ is AgBr and because
silver and bromide ions are present in a 1:1 ration in that compound, it follows
where the bracketed terms are molar species concentration. Also, we know that
From the last two equilibria, we see that the one hydroxide ion is formed
negative charge.
i) For Na+
= 1 X [Na+]
= 2 X [Mg2+]
= 3 X [PO43-]
and the H3O+ (from the dissociation of water). Negative charges are
supplied by the Cl- and the OH-. The molarities of positive and negative
charges are
unknown 's to be such that, when the 's are added to the original data,
, (137)
master species is added to the charge for that master species to remove
the equivalents for the element or element redox state that are already
accounted for in the alkalinity. For example, the contribution of carbonate
(http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/html/final-26.html)
Example 10-3
Example 10-4
constants.
defined in step 2.
computed in step 8.
10A-4) Making Approximations to Solve Equilibrium Equations
more easily.
simplified because they involve only sums and differences, not products
and quotients.
to many other species in the solution and the term for the
Example 10-5
As shown by the two equilibrium equations, there are two sources of hydroxide
ions: Mg(OH2) and H2O. The hydroxide ion resulting from the dissociation of
Mg(OH2) is twice the magnesium ion concentration and that from the dissociation
rigorously.
Step 7. Approximations
2[Mg2+] = [OH-]
gives
valid.
on pH.
Example 10-5
Calculate the molar solubility of calcium oxalate in a solution that has been
Oxalate ions react with water to form HC2O4- and H2C2O4. Thus, there three other
solubility = [Ca2+]
Because CaC2O4 is the only source of Ca2+ and the three oxalate species,
some weak acid HA and its conjugate base, A-. The identities of the three
species and their concentrations have not been specified, however, so we do not
We have four unknowns ([Ca2+], [H2C2O4], [HC2O4-], and [C2O42-]) as well as four
Step 7. Approximations
An exact solution is so readily obtained in this case that we will not bother with
approximations.
expression to give
[HC2O4-] = ([H3O+][C2O42-]) / K2
rearranging gives
[H2C2O4] = ([H3O+][C2O42-]•1.85) / K1
Substituting these expressions for [HC2O4-] and [H2C2O4] into the mass-balance
equation gives
or
Agents
soluble complexes.
Formation on Solubility
control over the reacting agent at a suitable and predetermined lever. This
Example 10-7
Calcium sulfide is less soluble than thallium sulfide (I). Find the condition under
which Cd2+ and Tl+ can, in theory, be separated quantitatively with H 2S from a
Since CdS precipitates at a lower [S 2-] than does Tl2S, we first compute the
when all but 1 part in 1000 of the Cd2+ has been removed; that is, the
[S2-] = 2 X 10-23
assume that quantitative removal of the cadmium will take place. Next, we
compute the [S2-] needed to initiate precipitation of Tl2S from a 0.1 M solution.
Precipitation will begin when the solubility product is just exceeded. Since the
(0.1)2[S2-] = 6 X 10-22
[S2-] = 6 X 10-20
These two calculations show that quantitative precipitation of Cd 2+ takes place if
[S2-] is made greater than 1 X 10-23. No precipitation of Tl+ occurs, however, until
Substituting these two values for [S 2-] into a previous equation permits the
[H3O+] = 3.5
and
[H3O+] = 0.045