4.

Solutions and their concentrations

4.1 Types of Solutions

Solvent

Solute

Solutions
Solutions are homogeneous mixtures of two or more pure substances. In a solution, the solute is dispersed uniformly throughout the solvent.

Solutions
The intermolecular forces between solute and solvent particles must be strong enough to compete with those between solute particles and those between solvent particles.

Dissolving process in water

How Does a Solution Form?

As a solution forms, the solvent pulls solute particles apart and surrounds, or solvates, them.

Orientation of water molecules around solute

2. Hydration of solute

Na+ 1. Overcome attractive forces in solid Cl6

Click here for Chime structure

Types of attractive forces

For water: dipole-dipole For hydrated ion: ion-dipole

How Does a Solution Form

If an ionic salt is soluble in water, it is because the iondipole interactions are strong enough to overcome the lattice energy of the salt crystal.

Na+ ClFor NaCl (s): ion-ion

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3 Stages of Solution Process

Separation of Solute
must overcome IMF or ion-ion attractions in solute requires energy, ENDOTHERMIC ( + H)

Energy Changes in Solution

Simply put, three processes affect the energetics of the process:
Separation of solute particles Separation of solvent particles New interactions between solute and solvent
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Separation of Solvent
must overcome IMF of solvent particles requires energy, ENDOTHERMIC (+ H)

Interaction of Solute & Solvent

attractive bonds form between solute particles and solvent particles 9 Solvation or Hydration (where water = solvent)

4.1 Types of Solutions

Saturated
Solvent holds as much solute as is possible at that temperature. Dissolved solute is in dynamic equilibrium with solid solute particles.

Types of Solutions
Unsaturated
Less than the maximum amount of solute for that temperature is dissolved in the solvent.

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Types of Solutions

4.2 Different ways of expressing concentration

Molarity (M) = Liter of solution = L

Supersaturated
Solvent holds more solute than is normally possible at that temperature. These solutions are unstable; crystallization can usually be stimulated by adding a seed crystal or scratching the side of the flask.
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2

Moles of solute

Mol
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amount of solute Parts ratio = amount of solution(g or ml) (10 ) or (10 ) or (10 ) (g or ml)

Mole Fraction Molality

Moles of solute ()= Total moles of solution Moles of solute

Kilograms of solvent
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(m) =

Molarity

Molarity

NaCl

Molarity

Example Problem 1

NaCl

Molarity

Example Problem 2

12.6 g of NaCl are dissolved in water making 344mL of solution. Calculate the molar concentration.

How many moles of NaCl are contained in 250.mL of solution with a concentration of 1.25 M?

M=

moles solute L solution

1molNaCl 12.6 g NaCl 58.44 gNaCl = 1L 344 mL solution 1000 mL

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M=

moles solute L solution

1L 250. mL = 0.250 L solution 1000mL

Volume x concentration

therefore the solution contains 1.25 mol NaCl 1 L solution

= moles solute

= 0.627 M NaCl

1.25 mol NaCl 0.250 L solution = 0.313 1 L solution

mol NaCl 16

Molarity
% (w/w) =
NaCl

% Concentration
mass solute mass solution mass solute volume solution x 100

Molarity

Example Problem 3

What volume of solution will contain 15 g of NaCl if the solution concentration is 0.75 M?

% (w/v) =

x 100

M=

moles solute L solution

therefore the solution contains 0.75 mol NaCl 1 L solution

1 mol NaCl 15 g NaCl = 0.257 mol 58.44 g NaCl

% (v/v) =

volume solute volume solution

x 100

moles solute concentration = volume solution

Mass and volume units must match. (g & mL) or (Kg & L)
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1 L solution 0.257 mol NaCl = 0.75 mol NaCl

0.34 L solution 17

Mass-Mass % Concentration

Mixing Solute and Solvent

Solute

Solvent 46.0 g H2O

mass/mass %

= g solute x 100% 100 g solution

4.0 g KCl

50.0 g KCl solution

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Calculating Mass-Mass %

Learning Check PC1

A solution contains 15 g Na2CO3 and 235 g of H2O? What is the mass % of the solution?

g of KCl g of solvent g of solution

= = =

4.0 g 46.0 g 50.0 g

1) 15% (m/m) Na2CO3 2) 6.4% (m/m) Na2CO3 3) 6.0% (m/m) Na2CO3

%(m/m) = 4.0 g KCl (solute) x 100 = 8.0% KCl 50.0 g KCl solution
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% Concentration
Solution PC1
mass solute = 15 g Na2CO3 15 g + 235 g = 250 g
% (w/v) =

Example Problem 1
What is the concentration in %w/v of a solution containing 39.2 g of potassium nitrate in 177 mL of solution?

mass solution =

%(m/m) = 15 g Na2CO3 250 g solution

100

39.2 g mass solute 100 = 22.1 % w/v 100 volume solution 177 mL

Example Problem 2
What is the concentration in %v/v of a solution containing 3.2 L of ethanol in 6.5 L of solution?

= 6.0% Na2CO3 solution

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% (v/v) =

volume solute 100 volume solution

3.2 L 100 6.5 L

= 49 % v/v
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% Concentration
Example Problem 3
What volume of 1.85 %w/v solution is needed to provide 5.7 g of solute?

Parts per million/billion (ppm & ppb)

ppm =

1.85 g solute % (w/v) = 100 mL solution

We know:
g solute and g solute mL solution

mass solute 106 volume solution mass solute 109 volume solution

or

mg = ppm L

We want to get:

ppb =

or

g
L

= ppb

mL solution

AND

100 mL solution 5.7 g solute 1.85 g solute

g solute concentration

Mass and volume units must match.

= 310 mL Solution
= volume solution
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(g & mL)

or

(Kg & L)
parts per trillion

For very low concentrations:

ng L

= ppt
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ppm & ppb

Example Problem 1
An Olympic sized swimming pool contains 2,500,000 L of water. If 1 tsp of salt (NaCl) is dissolved in the pool, what is the concentration in ppm?

ppm & ppb

Example Problem 2
An Olympic sized swimming pool contains 2,500,000 L of water. If 1 tsp of salt (NaCl) is dissolved in the pool, what is the concentration in ppb?

1 teaspoon = 6.75 g NaCl

or
mg solute ppm = L solution

1 teaspoon = 6.75 g NaCl

or
ppb =

g solute ppm = 106 mL solution ppm = 6.75 g 106 mL 2.5106 L ( 1000L ) 1

g solute ppb = 109 mL solution ppb = 6.75 g 109 mL 2.5106 L ( 1000L ) 1

g solute L solution

ppm =

6.75 g ( 1000gmg ) 1 2.5106 L

6.75 g ppb =

106 mg 1 g

2.5106 L
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ppm = 0.0027

ppm = 0.0027 27

ppb = 2.7

ppb = 2.7

Mole Fraction
B A A A B A B A A B A A B A

Mole Fraction
Example Problem 1
In our glass of iced tea, we have added 3 tbsp of sugar (C12H22O11). The volume of the tea (water) is 325 mL. What is the mole fraction of the sugar in the tea solution? (1 tbsp sugar 25 g) First, we find the moles of both the solute and the solvent.
1 mol C12 H 22 O11 75.g C12 H 22O11 = 0.21 9 mol 342 g C12 H22 O11
A

Mole Fraction () moles of A A = sum of moles of all components A

A

moles of B B B = sum of moles of all components

Since A + B make up the entire mixture, their mole fractions will add up to one.

1 mol H 2 O 325mL H 2 O = 18.1 mol 18.0 g H 2 O

Next, we substitute the moles of both into the mole fraction equation.

A + B = 1.00

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sugar =

0.219 mol sugar moles solute = (0.219 mol + 18.1 mol) total moles solution

= 0.012
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Mole Fraction
Example Problem 2
Air is about 78% N2, 21% O2, and 0.90% Ar. What is the mole fraction of each gas?
First, we find the moles of each gas. We assume 100. grams total and change each % into grams.

Molal (m)
Example Problem 1
If the cooling system in your car has a capacity of 14 qts, and you want the coolant to be protected from freezing down to -25F, the label says to combine 6 quarts of antifreeze with 8 quarts of water. What is the molal concentration of the antifreeze in the mixture?

1 mol N 2 1 mol O2 78g N 2 = 2.79 mol 21g O2 = 0.656 mol 28 g N 2 32 g O2

1 mol Ar 0.90g Ar = 0.0225 mol 40. g Ar

Next, we substitute the moles of each into the mole fraction equation.

m=

mol solute Kg solvent

antifreeze is ethylene glycol C2H6O2 1 qt antifreeze = 1053 grams 1 qt water = 946 grams

moles N 2 N2 = total moles

moles O 2 O2 = total moles 0.656 mol O 2

=

moles Ar Ar = total moles

0.0225 mol Ar

2.79 mol N 2
(2.79 + 0.656 + 0.0225)

m=

1053 g C 2H 6O2 1mol C 2 H 6 O2 6 Qts 1 Qt C 2H 6O2 62.1 g C 2 H 6 O2

946 g H 2 O 8 Qts 1 Qt H 2 O

(2.79 + 0.656 + 0.0225)

(2.79 + 0.656 + 0.0225)

= 0.804

= 0.189

= 0.00649
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1 Kg 1000 g

= 13 m
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4.3 Preparation of solutions

Solution preparation
We have two ways to prepare solutions according to the nature of substances.
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Solid state :
To prepare solution from solid so we must know the concentration which will be prepared in a certain volume.

liquid state :
To prepare solution from liquid state so we must know the molarity for the substance to help us to know density ( D ) purity ( P ) M = P D 10 / M.wt

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Preparation of solutions
How many grams of Potassium Dichromate, K 2Cr2O7, are required to prepare a 250mL solution with a concentration of 2.16M? 250mL x 1L/ 1000mL = .250L M= n/v n= M x v n= 2.16M x .250L n= 0.54 mol moles = g/MW Grams = moles x MW Grams = 0.54 mol K2Cr2O7 x 294.2 g K2Cr2O7 Grams = 159 159 grams of K2Cr2O7 are needed to prepare the requested 37 solution.

Preparation of solutions
In a biochemical assay, a chemist needs to add 0.381g of glucose to a reaction mixture. Calculate the volume in millimeters of a 2.53M glucose solution that she should use for this addition. moles = g/MW moles = 0.381g C6H12O6/ 180.2g C6H12O6 moles = 2.114 x 10 2 mol C6H12O6 M = n/v v = n/M v = 2.114 x 10 2 mol C6H12O6 / 2.53M C6H12O6 v = 8.36mL
38 She should use 8.36mL of the 2.53M glucose solution.

Preparation of Solutions
Explain the process of creating 1L of 3.0M KCl. M = n/v n=Mxv n = 3.0M x 1L n = 4.0 mol of KCl needed moles= g/MW Grams = moles x MW Grams = 4.0 mol KCl x 36.0g KCl Grams = 144g KCl Weigh out 144g of KCl. Put in a 1L flask. Add enough dH20 to dissolve KCl. Fill flask to 1L meniscus.

Dilution of Solutions
Dilution- the procedure for preparing a less concentrated solution from a more concentrated one. Dilutions can be made in increments of 10, 20, 50 or any other value. Serial Dilution- the process of diluting a solution by removing part of it, placing this in a new flask and adding water to a known volume in the new flask.

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Dilution of Solutions
When you want to dilute a solution, what happens to the number of moles present in the solution?
Do they increase? Decrease? Stay the same?

Dilution of Solutions

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Dilution of solutions
Since moles are constant before and after dilution, we can use the following formula for calculations.
MiVi = MfVf

Dilution of Solutions
Describe how you would prepare 800mL of a 2.0M H2SO4 solution, starting with a 6.0M stock solution of . 800mL x 1L/ 1000mL = 0.800L MiVi = MfVf 6.0M x Vi = 2.0M x 0.800L 6.0M x Vi = 1.6M x L Vi = 1.6M x L/ 6.0M Vi = 0.26L 0.26L of the 6.0M H2SO4 solution should be diluted to give a final volume of 800mL. 44

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EFFECT OF ELECTROLYTES ON CHEMICAL EQUILIBRIA

The position of most solution equilibria depends on the electrolyte concentration of the medium, even when the added electrolyte contains no ion in common with those involved in the equilibrium. H3AsO4 + 3I- + 2H+ H3AsO3 + I3- + H2O If an electrolyte, such as barium nitrate, potassium sulfate, or sodium perchlorate, is added to this solution, the color of the triiodide ion becomes less intense. This decrease in color intensity indicates that the concentration of I3- has decreased and that the equilibrium has been shifted to the left by the added electrolyte.
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How Do Ionic Charges Affect Equilibria? The magnitude of the electrolyte effect is highly dependent on the charges of the participants in an equilibrium. When only neutral species are involved, the position of equilibrium is essentially independent of electrolyte concentration. With ionic participants, the magnitude of the electrolyte effect increases with charge. In a 0.02 M solution of potassium nitrate, the solubility of barium sulfate is larger than it is in pure water by a factor of 2. The solubility of barium iodate by a factor of only 1.25 and that of 47 silver chloride by 1.2

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What Is the Effect of Ionic Strength on Equilibria? The effect of added electrolyte on equilibria is independent of the chemical nature of the electrolyte but depends on a property of the solution called the ionic strength. This quantity is defined as ionic strength = =1/2([A]ZA2 + [B]ZB2 + [C]ZC2 + ) Where [A], [B], [C], represent the molar species concentrations of ions A, B, C, and ZA, ZB, ZC, are their ionic charges. For solutions with ionic strengths of 0.1 M or less, the electrolyte effect is independent of the kind of ions and dependent only on the ionic strength. This independence with respect to electrolyte species disappears at high ionic strengths. 50

The Salt Effect The electrolyte effect results from the electrostatic attractive and repulsive forces that exist between the ions of an electrolyte and the ions involved in an equilibrium. These forces cause each ion from the dissociated reactant to be surrounded by a sheath of solution that contains a slight excess of electrolyte ions of opposite charge. When a barium sulfate precipitate is equilibrated with a sodium chloride solution, each dissolved barium ion is surrounded by an ionic atmosphere carries a small net negative charge. 51

continued

Each sulfate ion is surrounded by an ionic atmosphere that tends to be slightly positive. These charged layers make the barium ions somewhat less positive and the sulfate ions somewhat less negative than they would be in the absence of electrolyte. The consequence of this effect is a decrease in overall attraction between barium and sulfate ions and an increase in solubility, which becomes greater as the number of electrolyte ions in the solution becomes larger.
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ACTIVITY COEFFICIENTS

continued

Chemists use the term activity, a, to account for the effects of electrolytes on chemical equilibria. The activity, or effective concentration, of species X depends on the ionic strength of the medium and is defined as aX =x[X] where, aX is the activity of X, [X] is its molar concentration, and x is a dimensionless quantity called the activity coefficient.
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The activity coefficient and thus the activity of X vary with ionic strength such that substitution of aX for [X] in any equilibrium-constant expression frees the numerical value of the constant from dependence on the ionic strength. If XmYn is a precipitate, the thermodynamic solubility product expression is defined by the equation Ksp = aXm.aYn Ksp = Xm. Yn.[X]m[Y]n = Xm. Yn. K`sp Here K`sp is the concentration solubility product constant and Ksp is the thermodynamic equilibrium constant.
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Properties of Activity Coefficients

1. The activity coefficient of a species is a measure of the effectiveness with which that species influences an equilibrium in which it is a participant. In very dilute solution, where the ionic strength is minimal, this effectiveness becomes constant and the activity coefficient becomes unity. Under such circumstances, the activity and the molar concentration are identical (as are thermodynamic and concentration equilibrium constants). As the ionic strength increases, however, an ion loses some of its effectiveness and its activity coefficient decreases. At moderate ionic strengths, x < 1; as the solution approaches infinite dilution, however, x 1 and thus ax [X] and K`sp Ksp
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continued

The Debye-Huckel Equation

2. In solutions that are not too concentrated, the activity coefficient for a given species is independent of the nature of the electrolyte and dependent only on the ionic strength. 3. For a given ionic strength, the activity coefficient of an ion departs farther from unity as the charge carried by the species increases. The activity coefficient of an uncharged molecule is approximately unity, regardless of ionic strength. 4. At any given ionic strength, the activity coefficients of ions of the same charge are approximately equal. The small variations that do exist can be correlated with the effective diameter of the hydrated ions. 5. The activity coefficient of a given ion describes its effective behavior in all equilibria in which it participates. 57

P. Debye and E. Huckel derive a theoretical expression that permits the calculation of activity coefficients of ion from their charge and their average size. This equation takes the form

0.51Zx log x = 1 + 3.3 x

where, x = activity coefficient of the species X Zx = charge on the species X = ionic strength of the solution x = effective diameter of the hydrated ion X in nanometer (10-9 m) 58

continued

The constants 0.51 and 3.3 are applicable to aqueous solution at 25oC; The magnitude of x appears to be approximately 0.3 nm for most singly charged ions; then, the denominator of the Debye-Huckel equation simplifies to approximately 1 + . For ions with higher charge, x may be as large as 1.0 nm.

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Omitting Activity Coefficients in Equilibrium Calculations We shall ordinarily neglect activity coefficients and simply use molar concentrations in application of the equilibrium law. This recourse simplifies the calculations and greatly decreases the amount of data needed. For most purposes, the error introduced by the assumption of unity for the activity coefficient is not large enough to lead to false conclusions. Significant discrepancies occur when the ionic strength is large (0.01 or larger) or when the ions involved have multiple charges. With dilute solutions (ionic strength < 0.01) or nonelectrolytes or of singly charged ion, the use of concentrations in a mass-law calculation often provided reasonably accurate results.61

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