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4.1 Solutions and their concentrations
A solution is a homogeneous mixture of two or more substances.
A solution has two components namely, solute and solvent.
A solute is a substance that dissolves, existing in small proportion and the most active
component chemically.
A solvent is a substance that does the dissolving process, existing in larger proportion, Must
be greater than 50% of the solution. whose physical state doesn’t change during the solution
process and the least active component chemically.
Concentration: The relative amount of solute and solvent in a solution.
Based on the relative amount of solute in the solution, solutions may be dilute or
concentrated; unsaturated, saturated, or supersaturated.
Unsaturated solution : that contain the maximum amount of solute for a given amount of
solvent at a constant temp.
Saturated Solution: A solution that contains the maximum amount of a particular solute that will
dissolve at that temperature.
Supersaturated Solution: A solution that contains more solute than equilibrium conditions allow;
it is unstable and the solute may precipitate upon slight agitation or addition of a single crystal.
Degree of saturation is dependent on temperature;
2 e.g. more sugar will dissolve when tea is hot.
Types of Saturation
Kinds of Saturation Definition
A solution with solute that dissolves until
Saturated Solution it is unable to dissolve anymore, leaving
the undissolved substances at the bottom.
A solution (with less solute than the
saturated solution) that completely
Unsaturated Solution
dissolves, leaving no remaining
substances.
A solution (with more solute than the
saturated solution) that contains more
Supersaturated Solution undissolved solute than the saturated
solution because of its tendency to
crystallize and precipitate.
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Cont…
There are 9 types of solutions, based on the solute (1st) and the solvent (2nd)
Table 2.1 types of solutions with example:
solute gas gas gas liquid liquid liquid solid solid solid
solvent gas liquid solid gas liquid solid gas liquid solid
e.g.
air Soda H in H2O( Alcoh Silver S(v)i Sugar bras
H2O Pt v) in ol in amalg n air in s
air H2O am H2O
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4.2. Different ways of expressing concentration
The quantity of a solute in a given quantity (weight or volume) of the
solvent or solution is known as conc of a solution.
When we want to compare in a qualitative way the conc of solutions,
we use terms dilute and concentrated.
Quantitatively the conc of solution is expressed in terms of molarity,
normality, molality, mole fraction, percent by mass and volume, ppm,
etc.
Conc. can be expressed as the relative amount of solute per unit vol or
unit mass of solution.
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Common units of Concentration
7 Table 2.2. Common units of Concentration
1. Molarity (M)
Molarity is defined as the number of moles of a solute per liter of solution.
M= number of moles of solute/liters of solution
M = n/V
For preparation of so/n of any desired molarity (M) & volume (V):
Grams of solute = V X M X MW solute,
Where V = volume in liter; M = molarity and
MW solute means molecular weight of the solute.
Molarity is the most commonly used unit of conc.
e.g.-1: Calculate the number of moles and number of grams of KMnO4
([Link] =158) in 3.0 L of a 0.25 M solution.
Solution: n = M x v(L) = 0.25 mol/L x 3.0 L = 0.750 mol
mass in gram (m) = n x formula weight ([Link])
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= 0.750 mol x 158.0 g/mol = 119 g
e.g.-2 : 18g of sugar(sucrose(C6H12O6)) is dissolved in 500ml of water.
Calculate the conc of the solution in molarity?
(given [Link] of sucrose is 180g/mol)
Solution
n = given mass / molar mass = 18g / 180g/mol = 0.1 mole
M = number of moles / liter of solution = 0.1mole / 0.5L = 0.2M
Class work
Q-1: Calculate the mass of NaCl required to prepare 200ml of 0.2M of
NaCl solution?(given [Link] of NaCl is 58.5g/mol)
Answer :2.34g
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Q-2: Prepare 4.6 liter of 0.75M NaCl solution?
Answer:
Step-1: Calculate the mass of NaCl, molar mass 58.5g/mol required.
0.750mol/L = Mass solute/(58.5g/mol x4.60L)
Mass solute = 0.75mol/L x 58.5g/mol x4.60L = 202g
Step-2: Weight out 202 g NaCl
Step-3: Add NaCl to a container with mark at 4.60 L
Step-4: Add water and mix to a final volume of 4.60L
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Cont…
In practice, a solution of known molarity is prepared by weighing an
appropriate amount of solute and placing it in a volumetric flask.
Enough solvent is added to dissolve the solute, & further solvent is added
until an accurately calibrated final volume is reached.
The so/n is then shaken until it is uniformly mixed as show in figure.
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[Link]
N is the number of equivalents of solute per liter of solution
N = No. of equivalents/ liter of solution
No. of equivalents = given mass /equivalent weight.
Equivalent weight = formula mass / n.
“n” is a rxn unit which has different values for different reactions .
In an acid–base rxn, the rxn unit is the number of H+ ions donated
by an acid or accepted by a base.
H2SO4 (aq) + 2NH3 (aq) 2NH4 + (aq) + SO42–(aq)
We find that n = 2 for H2SO4 and n = 1 for NH3
In a precipitation rxn, the rxn unit is the charge of the cation or anion
involved in the rxn; thus for the rxn
Pb2+ (aq) + 2I–(aq) PbI2(s) n = 2 for Pb2+ and n = 1 for I–.
Finally, in an oxidation–reduction rxn the rxn unit is the number of
electrons released by the reducing agent or accepted by the oxidizing
agent; thus, for the rxn
2Fe3+ (aq) + Sn2+ (aq) Sn4+ (aq) + 2Fe2+ (aq)
n = 1 for Fe3+ and n = 2 for Sn2+.
The ff simple relationship exists between N & M.
N=nXM
Eg, what is the N of 2M H2SO4?
Ans. 4N
Eg. : Calculate the normality of a solution of HCl containing
2.2g of Hydrogen chloride in 200mL.
Solution: Volume of the solution = 200mL = 0.20L
Number of equivalents of HCl = actual mass /equivalent wt of HCl
= 2.2g/36.5g/equivalent
= 0.06 equivalent
Normality = no of equivalents / Liters of solution
= 0.06equivalents / 0.20L
= 0.3 equivalents/L = 0.3N
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3. Molality(m)
Molality is the mole of the solute per kilogram of the solvent.
m = mole of solute / kg of solvent
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Q1:A 4 g sugar cube (Sucrose: C12H22O11) is dissolved in a 350 ml teacup of 80
°C water. What is the molality of the sugar solution?
Given: Density of water at 80° = 0.975 g/ml
Solution;
Molality is the number of moles of solute per kilogram of solvent.
Step 1 - Determine number of moles of sucrose in 4 g
Solute is 4 g of C12H22O11
C12H22O11 = (12)(12) + (1)(22) + (16)(11) = 342 g/mol
n = 4 g /(342 g/mol) = 0.0117 mol
Step 2 - Determine mass of solvent in kg.
density = mass/volume
mass = density x volume
mass = 0.975 g/ml x 350 ml= 341.25 g= 0.341 kg
Step 3 - Determine molality of the sugar
molality = molsolute / masssolvent
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molality = 0.0117 mol / 0.341 kg= 0.034 mol/kg
4. Percent by mass and volume:
% composition may be the % of the solute relative to the final solution
on either weigh-by-weight or volume- by- volume basis.
i. volume/volume (%v/v) = Volume of solute x 100/Volume of so/n
For preparation: Vol to measure = (% desired/100) X so/n vol desired
ii. weight/weight (%w/w) = Weight of solute x 100/ mass of total so/n
For prepn: Weight to measure = (% desired/100) x so/n weight desired
iii. weight/volume (%w/v) = Weight of solute x 100/Volume of so/n
For prepn: Weight to measure =(% desired/100) x so/n vol desired
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E.g. A concentrated so/n of aqueous NH3 is 28.0% w/w NH3 & has a density
of 0.899g/mL. what is the molar conc of NH3 in this so/n?
Solution:
i) 28%w/w mean there is 28g NH3 in 100g of solution
ii) density of 0.899g/mL mean the mass of so/n is 0.899g in 1ml so/n.
From this two data we can easily calculate the volume of the so/n.
Vol of so/n = mass of so/n / density = 100g/.0899g/mL = 111.235mL
M = [Link] NH3 /([Link] NH3 X Vol. of so/n in L
= 28g of NH3 /(17.04 g/mol X 0.111235L) = 14.77M
Q-1: Find the M and m of 37.0 wt% HCl (36.46g/mol). The density of a
substance is the mass per unit vol. of the reagent is equal to 1.19 g/ml.
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Ans =12.1M and 16.1m (Hint. Solvent = so/n – solute )
Diluting Solutions
Often it is necessary to make a less concentrated solution from a more
concentrated solution; this process is called dilution.
This situation usually occurs in the laboratory because it is more convenient
to store more-concentrated so/ns in order to save shelf space.
Also, laboratory acid so/ns, such as those of HCl, H2SO4, & H3PO4, are
almost always purchased as highly concentrated solutions; these are more
economical because there is more of the active ingredient per bottle.
Using subscripts To indicate values before and after dilution, respectively.
M1 = (Moles solute)1/(Volume solution)1
M2 = (Moles solute)2/(Volume solution)2
And setting “Moles solute” before & after dilution equal to each other:
M1 X (Volume solution)1 = M2 X (Volume solution)2
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(Volume solution)1 = M2 X (Volume solution)2 / M1
Example:1) The conc of commercial concentrated HCl is 12 M. A
laboratory technician needs 1 liter of 1 M HCl. How much of the
concentrated acid is required?
Solution ;
, V= 0.08 L
2)What is the molarity of a solution prepared by diluting 10.00 mL of a
4.281 M solution to 50.00 mL?
Solution
Using Equation , we have the following:
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At the equivalence point of a titration, exact stoichiometric amounts of the
reactants have reacted.
i.e. the amount of titrant(T)(dispensed via the buret, known) added is the
exact amount required to consume the amount of substance
titrated(ST)(solution held in the reaction flask) in the reaction flask.
If the reaction is one-to-one in terms of moles
HCl + NaOH → NaCl + H2 O (one hydrogen lost by HCl)
If the reaction is two-to-one in terms of moles , then the moles of titrant is
twice the moles of substance titrated:
H2SO4 + 2NaOH → Na2SO4 + 2H2O (two hydrogens lost by H2SO4)
The moles of substance titrated is half the moles of titrant:
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or vice versa, depending on which substance is the titrant and
which is the substance titrated.
And so it goes for three-to-one, three-to-two, etc., reactions.
In general terms, then, we have the following:
or
Example
1) Standardization of a solution of sulfuric acid required 29.03 mL
of 0.06477 M NaOH when exactly 25.00 mL of H2SO4 was used.
What is the molarity of H2SO4?
Solution
22 H2SO4 + 2NaOH → Na2SO4 + 2H2O (two hydrogens lost by H2SO4)
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ACTIVITY AND ACTIVITY COEFFICIENT
The attraction of the ions of the equilibrium reaction by the
dissolved electrolyte effectively shield them, decreasing their
effective concentration and shifting the equilibrium. effective
concentration of an ion in the presence of an electrolyte is called
the activity of the ion.
Activity can be used to describe quantitatively the effects of salts
on equilibrium constants.
The activity of an ion ai is defined by
where Ci is the concentration of the ion and
fi is its activity coefficient.
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Ionic Strength - I
I = 1/2 S mi • Zi2
charge of i th ion
concentration of i th ion
The ionic strength has concentration units.
Example:. Molality
Seawater (SW) Lake Water (LW)
Na+ 0.49 0.2 x 10-3
Mg2+ 0.053 0.14 x 10-3
Ca2+ 0.010 0.22 x 10-3
K+ 0.010 0.03 x 10-3
Cl- 0.57 0.09 x 10-3
SO42- 0.028 0.102 x 10-3
HCO3- 0.002 0.816 x 10-3
ISW = 1/2 (mNa x 12 + mMg x 22 + mCa x 22 + mK x 12 + mCl x 12 + mSO4 x 22 + mHCO3 x 12)
= 0.72 mol kg-1
ILW = 0.0015 = 1.5 x 10-3 mol kg-1
The ionic strength µ is the measure of total electrolyte concentration and
is defined by
where µ is the ionic strength, Zi is the charge on the individual ion. All
cations and anions present in the solution are included in the calculation.
Example 1: Calculate the ionic strength of 0.20M solution of KNO3 and
0.20M solution of K2SO4.
Solution: For KNO3 µ = ½ ΣCiZ2i = ½ (CK+Z2K+ + CNO3-Z2NO3-)
= ½ ( 0.2 x (1)2 + 0.2 x(1)2)
= 0.2
For K2SO4 µ = ½ ΣCiZ2i = ½ (CK+Z2K+ + CSO42-Z2- SO42-
[K+] = 0.4M (2k+*0.2) [SO42-] = 0.2M
µ = ½ (0.4 x (1)2 + 0.2 x(2)2) = 0.6
Note that due to the doubly charged SO42-, the ionic strength of the
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K2SO4 is three times that of the KNO3.
How is the activity coefficient (fi) calculated?
The equation known as the Deybe-Huckel equation, is
Example 2: Calculate the activity coefficients for K+ and SO42- in a
0.20M solution of potassium sulfate.
Solution: From example 1, the ionic strength is 0.60 ( = 0.60)
Activity coefficient for K+
Activity coefficient for SO42-
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