PBL 3 REPORT

Case of Kidney Stones Formation and Solubility of Salt

GROUP 3

Baghaskara Surendra

1506710922

Muhammad Naufal Fadhila

1506712026

Raisya Afifah

1606862841

Muhammad Ivan Farhan

1606862854

Dian Ratri Cahyani

1606896981

FACULTY OF ENGINEERING
INTERNATIONAL PROGRAM
UNIVERSITAS INDONESIA
DEPOK 2016

1. Introduction
The kidney stones formation involved important reaction which is known as
precipitation reaction. The precipitation reaction occurred, when cations and anions combined
and formed an insoluble ionic solid in aqueous solution called as a precipitate. Precipitate has
similarity with solubility, which is has an ability of a substance to dissolve.
2. Theory

Kidney Stones

Kidney stones (renal lithiasis, nephrolithiasis) are small, hard mineral deposits that
form inside your kidneys. The stones are made of mineral and acid salts.
Kidney stones have many causes and can affect any part of your urinary tract from
your kidneys to your bladder. Often, stones form when the urine becomes concentrated,
allowing minerals to crystallize and stick together.
A kidney stone may not cause symptoms until it moves around within your kidney or
passes into your ureter the tube connecting the kidney and bladder. At that point, you may
experience these signs and symptoms:

Severe pain in the side and back, below the ribs

Pain that spreads to the lower abdomen and groin

Pain that comes in waves and fluctuates in intensity

Pain on urination

Pink, red or brown urine

Cloudy or foul-smelling urine

Nausea and vomiting

Persistent need to urinate

Urinating more often than usual

Fever and chills if an infection is present

Urinating small amounts of urine

Pain caused by a kidney stone may change for instance, shifting to a different location or
increasing in intensity as the stone moves through your urinary tract.
Kidney stones often have no definite, single cause, although several factors may
increase your risk.

Kidney stones form when your urine contains more crystal-forming substances
such as calcium, oxalate and uric acid than the fluid in your urine can dilute. At the same
time, your urine may lack substances that prevent crystals from sticking together, creating an
ideal environment for kidney stones to form.
Knowing the type of kidney stone helps determine the cause and may give clues on
how to reduce your risk of getting more kidney stones. Types of kidney stones include:

Calcium stones. Most kidney stones are calcium stones, usually in the form of
calcium oxalate. Oxalate is a naturally occurring substance found in food. Some fruits
and vegetables, as well as nuts and chocolate, have high oxalate levels. Your liver also
produces oxalate. Dietary factors, high doses of vitamin D, intestinal bypass surgery
and several metabolic disorders can increase the concentration of calcium or oxalate
in urine. Calcium stones may also occur in the form of calcium phosphate.

Struvite stones. Struvite stones form in response to an infection, such as a urinary

tract infection. These stones can grow quickly and become quite large, sometimes
with few symptoms or little warning.

Uric acid stones. Uric acid stones can form in people who don't drink enough fluids
or who lose too much fluid, those who eat a high-protein diet, and those who have
gout. Certain genetic factors also may increase your risk of uric acid stones.

Cystine stones. These stones form in people with a hereditary disorder that causes the
kidneys to excrete too much of certain amino acids (cystinuria).

Other stones. Other, rarer types of kidney stones also can occur.

Calcium oxalate is a very common kidney stone and its build up in the body can be
explained through equilibrium shifts in the body. One common chemical equation which can

be used to describe the relationship of kidney stones to equilibrium is CaC2O4(s)Ca+2 (aq)

+ C2O42- (aq).
Depending on the various factors that affect equilibrium and Le Chatleliers Principle,
the system will either shift towards the left, right or remain the same to obtain equilibrium.
Some of these factors include temperature, concentration, pressure, and volume. The Ksp
expression for this reaction would be Ksp= [Ca+2] [ C2O42-]. As you can see, this reaction is
very dependent on the concentration of calcium ions and oxalic acid in the kidney.

Precipitation

Precipitation reactions occur when cations and anions in aqueous solution combine to
form an insoluble ionic solid called a precipitate. Whether or not such a reaction occurs can
be determined by using the solubility rules for common ionic solids. Because not all aqueous
reactions form precipitates, one must consult the solubility rules before determining the state
of the products and writing a net ionic equation. The ability to predict these reactions allows
scientists to determine which ions are present in a solution, and allows industries to form
chemicals by extracting components from these reactions.
Precipitates are insoluble ionic solid products of a reaction, formed when certain
cations and anions combine in an aqueous solution. The determining factors of the formation
of a precipitate can vary. Some reactions depend on temperature, such as solutions used for
buffers, whereas others are dependent only on solution concentration. The solids produced in
precipitate reactions are crystalline solids, and can be suspended throughout the liquid or fall
to the bottom of the solution. The remaining fluid is called supernatant liquid. The two
components of the mixture (precipitate and supernate) can be separated by various methods,
such as filtration, centrifuging, or decanting.

Figure 1: Above is a diagram of the formation of a precipitate in solution.

The use of solubility rules requires an understanding of the way that ions react. Most
precipitation reactions are single replacement reactions or double replacement reactions.
A double replacement reaction occurs when two ionic reactants dissociate and bond with the
respective anion or cation from the other reactant. The ions replace each other based on their
charges as either a cation or an anion. This can be thought of as "switching partners"; that is,
the two reactants each "lose" their partner and form a bond with a different partner:

Figure 2: A double replacement reaction

A double replacement reaction is specifically classified as a precipitation
reaction when the chemical equation in question occurs in aqueous solution and one of the of
the products formed is insoluble.

Both reactants are aqueous and one product is solid. Because the reactants are ionic
and aqueous,

they dissociate

and

are

therefore soluble.

However,

there

are

six

solubility guidelines used to predict which molecules are insoluble in water. These molecules
form a solid precipitate in solution.

Net Ionic Equations

To understand the definition of a net ionic equation, recall the equation for the
double replacement reaction. Because this particular reaction is a precipitation reaction, states
of matter can be assigned to each variable pair:
AB(aq) + CD(aq) AD(aq) + CB(s)
The first step to writing a net ionic equation is to separate the soluble (aqueous)
reactants and products into their respective cations and anions. Precipitates do not dissociate
in water, so the solid should not be separated. The resulting equation looks like that below:
A+(aq) + B-(aq) + C+(aq) + D-(aq) A+(aq) + D-(aq) + CB(s)
In the equation above, A+ and D- ions are present on both sides of the equation. These
are called spectator ions because they remain unchanged throughout the reaction. Since they
go through the equation unchanged, they can be eliminated to show the net ionic equation:
C+ (aq)+ B- (aq) CB (s)
The net ionic equation only shows the precipitation reaction. A net ionic equation
must be balanced on both sides not only in terms of atoms of elements, but also in terms of
electric charge. Precipitation reactions are usually represented solely by net ionic equations.
If all products are aqueous, a net ionic equation cannot be written because all ions are
canceled out as spectator ions. Therefore, no precipitation reaction occurs.

Solubility

Solubility is the ability of a solid, liquid, or gaseous chemical substance (referred to as

the solute) to dissolve in solvent (usually a liquid) and form a solution. The solubility of a
substance fundamentally depends on the solvent used, as well as temperature and pressure.
The solubility of a substance in a particular solvent is measured by the concentration of
the saturated solution. A solution is considered saturated when adding additional solute, no
longer increases the concentration of the solution.
The degree of solubility ranges widely depending on the substances, from infinitely
soluble (fully miscible), such as ethanol in water, to poorly soluble, such as silver chloride in

water. The term "insoluble" is often applied to poorly soluble compounds. Under certain
conditions, the equilibrium solubility can be exceeded, yielding a supersaturated solution.
Solubility does not depend on particle size; given enough time, even large particles will
eventually dissolve.
Factors affecting solubility:
Temperature - solubility tends to correspond with increasing temperature.
Pressure - solubility of gases tends to correlate with increasing pressure.
Polarity - the ability for a solvent to dissolve various compounds depends

primarily on its polarity.

Stirring stirring increases the speed of the process, increases the movement of

the solvent.
Molecular size small molecular weight is easier to dissolve.

Solubility product constant

The solubility product constant, Ksp, is the equilibrium constant for a solid substance

dissolving in an aqueous solution. It represents the level at which a solute dissolves in

solution. The more soluble a substance is, the higher the Ksp value it has. Consider the
general dissolution reaction below (in aqueous solutions):
aA(s)cC(aq)+dD(aq)
To solve for the Ksp it is necessary to take the molarities or concentrations of the
products (cC and dD) and multiply them. If there are coefficients in front of any of the
products, it is necessary to raise the product to that coefficient power (and also multiply the
concentration by that coefficient). This is shown below:
Ksp=[C]c[D]d(2)
Note that the reactant, aA, is not included in the Ksp equation. Solids are not
included when calculating equilibrium constant expressions, because their concentrations do
not change the expression; any change in their concentrations are insignificant, and therefore

omitted. Hence, Ksp represents the maximum extent that a solid that can dissolved in
solution.
The equilibrium constants for saturated solution and solid formation (precipitate) are
called Ksp. For unsaturated and supersaturated solutions, the system is not equilibrium and
ion products, Qsp, which have the same expression as Ksp is used.
Thus the relationship among Qsp, Ksp, and saturation;
Qsp < Ksp

Unsaturate solution

Qsp = Ksp

Saturate solution

Qsp > Ksp

Oversaturate solution

3. Assignments

1. How Indri and Betti will explain about the kidney stones?
What? stone that is consist of of the waste products in our blood and like a crystal stone
that blocks the urinary system.
How? The waste products precipitate and create a crystalize stone that block the system.
When? when someone lack of water or dehydration.
Where? The urinary system, ureter and urethra.
Who? People at age between 30 to 60.
2. How compounds in medication (drugs) can dissolve the calcium oxalate stones?
A deficiency in magnesium encourages the development of calcium oxalate stones.
Magnesium remains in a state of constant rivalry with calcium, reducing their chances of
binding with oxalates to form calculus.

Potassium citrate. Citrate can detach calcium oxalate stones from the urinary system and
dissolve them.
3. Chemical reaction involved in the formation & dissolution of Kidney Stones?
One common chemical equation which can be used to describe the relationship of kidney
stones to equilibrium is CaC2O4(s)Ca+2 (aq) + C2O42- (aq). This reaction shows the
reversible reaction of solid calcium oxalate breaking down into calcium ions and oxalic
acid or vise versa. Kidney stones are crystals of calcium oxalate (CaC2O4) and they form
when oxalic acid is present. The oxalic acid in the body reacts with the calcium ions
found in the kidney to form calcium oxalate solids (or crystals) in the kidney. Depending
on the various factors that affect equilibrium and Le Chatleliers Principle, the system will
either shift towards the left, right or remain the same to obtain equilibrium. Some of these
factors include temperature, concentration, pressure, and volume. The Ksp expression for
this reaction would be Ksp= [Ca+2] [ C2O42-]. As you can see, this reaction is very
dependent on the concentration of calcium ions and oxalic acid in the kidney.

4. Write balanced equations of three reactions involved in their experiment?

First, metallic Calcium will be treated with aqueous Hydrochloric Acid. The acid will
oxidize the Calcium to Calcium Chloride. Hydrogen gas will be given off as a by-product.
Ca(s) + 2 HCl (aq) CaCl2(aq) + H2(g)

The resulting chloride salt is then treated with Ammonium Oxalate to form the final
product.
CaCl2(aq) + (NH4)2C2O4(aq) CaC2O4(s) + 2 NH4Cl(aq)
Aqueous Ammonia is added to this reaction mixture to prevent the excess Hydrochloric
Acid present from reacting with the Oxalate Ion. Also, the Calcium Oxalate actually
crystallizes out of solution as a hydrate;
CaC2O4 + H2O(s) CaC2O4H2O(s)

5. In that experiment, they react 3 g calcium powder with 100 ml of hydrochloric

acid solution 1 M. the calcium chloride formed react with 50 ml of ammonium
oxalate solution 0.5 M that is added to this solution. How many gram of calcium
oxalate monohydrate formed as the end product?
Ca (s) + 2 HCl (aq) CaCl2(aq) + H2(g)
M 0.075

0.1

0.1

0.05

0.05

nCa =

m
3
= =0.075
Ar 40

0.05
nHCL = M . V = 100 . 1 = 100 mmoles

0.025

0.05

0.05

CaCl2(aq) + (NH4)2C2O4(aq) CaC2O4(s) + 2 NH4Cl (aq)

M 0.05

0.025

R 0.025

0.025

0.025

0.05

S 0.025

0.025

0.05

n(NH4)2C2O4 = M.v = 50 . 0.5 = 25 mmol

Since we have gotten the moles for CaC2O4 which is 0.025, then to determine the mole for
CaC2O4H2O we could use its coefficient ratio from this reaction below:
CaC2O4 + H2O(s) CaC2O4H2O(s)
The coefficient in the reaction are all 1 so it means it the mole for CaC 2O4 could be use for the
mole of CaC2O4H2O.
Then we can get the mass by
m CaC2O4H2O = n . Mr = 0.025 . 146 = 3.65 grams
6. If ksp at 25c of CaCO is known, what is the minimum concentration of
calcium and oxalate ion in the water at 25c to precipitate calcium oxalate?
Ksp = [Ca] [CO] = s x s = s
To precipitate, Q > Ksp
[Ca] [CO] > Ksp
S2 > Ksp
To find the concentration for Calcium and Oxalate to precipitate
S=

Ksp
7. If a certain amount of oxalate ions is added to a solution mixture of calcium and
magnesium ions, which salt of oxalate will be first precipitated? Why?
The first that will be precipitate is Magnesium. The reason is as we can see from this

data of oxalate solubility [ Ca > Cd > Zn > {Mn, Ni, Fe, Cu} > {As, Sb, Pb} > Hg ] we can
see that calcium is more soluble than magnesium which in this case of precipitation. The
more insoluble the substance is, the higher the precipitation.

8. 10 gram of magnesium chloride hydrate, MgCl2(H20)6 is dissolved in 100 ml

water, is reacted with 100 ml solution of ammonium oxalate 1M to form
magnesium oxalate dehydrate, MgC2O4. (H2O)2. How many grams of this
hydrates formed and how many moles of unreacted ammonium oxalate in the
solution (molar)?

MgCl2(H20)6 is dissolved in water, the reaction would be;

MgCl2(H20)6 MgCl2 + 6H2O
10
203

Mole MgCl2(H20)6 =

= 0.049 = 0.05

MgCl2(H20)6 MgCl2 + 6H20

0.05

0.05

0.3

Mole (NH4)2C2O4 = M x V = 100 x 1 = 100 mmole = 0.1 mole

then we make the next reaction;
MgCl2 + (NH4)2C2O4 + 6H2O MgC2O4.(H2O)2 + 2ClNH4 + 2H2O
M

0.05

0.1

0.05

0.05

0.05

0.1

0.1

0.05

0.05

0.1

0.1

MgC2O4(H2O)2 formed, 0.05 moles. Convert it into grams;

Mass = n x Mr = 0.05 x 148 = 7.4 grams
Unreacted ammonium,
M=

n
V total

0.05
200 x 103

= 0.25 M

9. How do you describe the difference between Saturation-Super saturation;

Suspension-Precipitation; and factors affecting the precipitation or solubility?
Difference between Precipitation-Suspension

Precipitation = Formation of solid in a solution or inside solid during a chemical reaction or

by diffusion in a solid. When the reaction occurs in a liquid, the solid is called the precipitate
and the liquid above is called supernate
Suspension= A suspension is a heterogeneous mixture in which solute-like particles settle
out of a solvent-like phase some time after their introduction. We apply the word 'suspension'
when particles are big enough to eventually settle. If the particles are too small to ever settle,
they are said to form a colloid
Simpler way to describe suspension:
In chemistry, a suspension is a mixture of two or more components. In a suspension, very
small pieces of solid are spread through a liquid but do not dissolved. If left still, the solid
pieces will separate from the liquid and either fall to the bottom or rise to the
top. Sand in water is an example of suspension. Suspensions may separate quickly or stay
suspended for a long time, depending on what they contain.
Difference between Saturated, Supersaturated, Unsaturated:
Saturated Saturated solution is when the solute can dissolve in the solvent, for example, if
you have a bottle water and you pour a lemonade crystals into the water, and it dissolves, the
solution is saturated.
Unsaturated A supersaturated solution is when you pour the solute into the solvent and the
solute doesnt dissolve.
Supersaturated A supersaturated solution is a solution with more dissolved solute than
the solvent would normally dissolve in its current conditions.
10. In precipitation, there is phenomenon called the common ion effect. Give
example of this phenomenon with calculation.
The solubility products Ksps are equilibrium constants in heterogeneous equilibria.
If the salts contain a common cation or anion, these salts contribute to the concentration
When NaCl and KCl are dissolved in the same solution, the Cl- ions are common ion
La Chateliers principle states that if an equilibrium becomes unbalance, the reaction will shift
to restore the balance. If a common ion is added to a weak acid or weak base equilibrium,
then the equilibrium will shift towards the reactants.
Example;

PbCl2 Pb2+ + 2Cl[Pb2+] = s

[Cl-] = 2s
Ksp= [Pb2+][Cl-]2 = s x (2s)2
1,7 x 10-5 = 4s3
S3 = 1.7 x 10-5 / 4 = 4.25 x 10-6
S = 1.62 x 10-2 mol

11. Determine the pH range that would precipitate as all hydroxides of these heavy
metal ions but doesnt precipitate magnesium and calcium hydroxides. The
unbalance reaction of these metal hydroxides and Ksp are shown below.
Ca(OH)2 (s) Ca2+(aq) + OH-(aq)

Ksp = 1.3 x 10-6

Cd(OH)2 (s) Cd2+(aq) + OH-(aq)

Ksp = 5.9 x 10-15

Mg(OH)2 (s) Mg2+(aq) + OH-(aq) Ksp = 8.9 x 10-12

Mn(OH)2 (s) Mn2+(aq) + OH-(aq) Ksp = 1.9 x 10-13
Pb(OH)2 (s) Pb2+(aq) + OH-(aq)

Ksp = 1.2 x 10-15

Group of students are working in the lab to have experiments on precipitation. They
have industrial waste water with heavy-metal pollutants. The objectives are to
precipitate cadmium, lead and manganese at concentration of approximately 0.02 M
but let magnesium and calcium ions which concentrations are 0.005 M still in
solution
First, we need to balance the equations and determine what is the [OH-] concentration of each
reaction that precipitate the hydroxides

Ca(OH)2 Ca2+ + 2OH-

Ksp = 1.3 x 10-6 = [Ca2+][OH-]2

[OH-]=

1.3 x 1 06
0.005

= 0.016 M

Cd(OH)2 Cd2+ + 2OH-

Ksp = 5.9 x 10-15 = [Cd2+][OH-]2

[OH-]=

5.9 x 1 015
0.02

= 5.43 x 10-7 M

Mg(OH)2 Mg2+ + 2OH-

Ksp = 8.9 x 10-12 = [Mg2+][OH-]2

[OH-]=

8.9 x 1 012
0.005

= 4.22 x 10-5 M

Mn(OH)2 Mn2+ + 2OH-

Ksp = 1.9 x 10-13 = [Mn2+][OH-]2

[OH-]=

5.9 x 1 013
0.02

= 3.08 x 10-6 M

Pb(OH)2 Pb2+ + 2OH-

Ksp = 1.2 x 10-15 = [Pb2+][OH-]2

[OH-]=

1.2 x 1 015
0.02

= 2.45 x 10-7 M

pH range that would precipitate hydroxides (except Mg and Ca): 7.4 < pH < 8.5 (pH is
greater than 7.4 and less than 8.5)

Ca[OH-] = 0.016M

pOH = -log[OH-] = -log(0.016) = 1.7

pH = 12.2

Cd[OH-] = 5.43 x 10-7 M

pOH = -log[OH-] = -log(5.43 x 10-7) = 6.2

pH = 7.7

Mg[OH-] = 4.22 x 10-5 M

pOH = -log[OH-] = -log(4.22 x 10-5) = 4.4

pH = 9.6

Mn[OH-] =3.08 x 10-6 M

pOH = -log[OH-] = -log(3.08 x 10-6 ) = 5.5

pH = 8.5 (max[OH-])

Pb[OH-] = 2.45 x 10-7 M

pOH = -log[OH-] = -log(2.45 x 10-7 ) = 6.61

pH = 7.4 (min [OH-])

References:
-

Chemistry the Central Science 13th edition

Chem.libretext.org
http://infohost.nmt.edu/~jaltig/CalciumOxalate.pdf
http://www.chem1.com/acad/webtext/solut/solut-6a.html