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1 
Chapter 4
2 
Many chemical reactions and virtually all biological processes take 
place in water. 
e.g.: all chemistry that makes life possible occur in aqueous solution, 
various medical tests involve aqueous reactions like sugar 
tests..cholesterol .. ect 
To understand the chemistry that occur in such diverse places as 
human body, the atmosphere, the ground water, the oceans, and so 
on, we must understand how substances dissolved in water react with 
each other.
3 
Before we can understand solution reactions, we need to 
discuss the nature of solutions in which water is the 
dissolving medium or solvent. 
These solutions- (homogeneous mixture) are called aqueous 
solutions. 
aqueous solutions 
Solvent Solute what gets 
Soluble- Can be dissolved. 
Miscible- liquids dissolve in each other. 
dissolved 
what does the 
dissolving
4 
Water, the common solvent 
 One of the most valuable properties of water 
is ability to dissolve many different 
substances. 
 Water is a good solvent for ionic compounds 
because its molecules are polar. The oxygen 
atoms have a partial negative charge. The 
hydrogen atoms have a partial positive 
charge. 
 The angle is 104.5ºC. 
 It is the polarity that gives water its great 
ability to dissolve compounds 
+ δ 
+ δ 
-δ
5 
 A schematic of an ionic solid dissolving in water is 
shown in the following figure. 
 The “positive ends” of water molecules are attracted to 
the negatively charged anions and the “negative ends” are 
attracted to the positively charged cations 
 This process is called hydration 
 The hydration process is breaking the ionic substances 
(salts) apart into individual cations and anions and 
surrounded by water molecules 
 When NaCl dissolves in water, the resulting solution 
contains Na+ and Cl- ions moving around independently. 
NaCl(s) Na+ 
(aq) + Cl- 
H (aq) 2O(ℓ)
How Ionic solids dissolve 
H H 
O 
6 
O 
H H 
H H 
O 
O 
H H 
H H 
O 
H H 
O 
O 
H H 
H H 
O 
H 
O 
H
7 
 The solubility is how much of a substance will dissolve 
in a given amount of water, usually g/100 mL 
 The solubility of ionic substances in water varies greatly, 
e.g: NaCl soluble in water, whereas AgCl insoluble in 
water 
 If the ionic substance do dissolve the ions are separated, 
and they can move around. 
 Water can also dissolve non-ionic compounds if they 
have polar bonds like ethanol (C2H5OH). 
 “Like dissolve like” is a useful rule for predicting 
solubility.
8 
Types of solutions 
Solutions are classified three ways 
 Strong electrolytes- completely dissociate (fall apart into 
ions). - Many ions - Conduct electricity well. 
e.g.: NaCl give Na+ , Cl- when dissolve in water 
 Weak electrolytes- Partially fall apart into ions. 
– Few ions -Conduct electricity slightly. 
e.g.: acetic acid dissociate partially in water. 
 Non-electrolytes- Don’t fall apart. - No ions- Don’t 
conduct electricity. 
e.g.: sugar ( C12H22O12) , ethanol (C2H5OH)
9 
The composition of solution 
Chemical reactions take place when two solution are mixed. 
To perform stoichiometric calculations in such cases, two 
things must be known: 
1.The nature of the reaction 
2.The amount of chemicals present in the solution, expressed 
as concentrations. 
Concentration: is how much solute is dissolved in a given 
amount of solvent. 
The concentration of solution can be expressed in many 
different ways. We will consider only the most commonly 
used expression of concentration, molarity
Molarity (M): moles of solute per volume of solution in liters 
1 M = 1 mol solute / 1 liter solution 
1 M = 1 mol solute dissolved water until the volume of solute and 
solvent (solution) become 1 liter 
The concentration is an intensive property, so its value does not 
depend on how much of the solution is present. 
Example (1): 
Calculate the molarity of a solution with 34.6 g of NaCl (molar mass = 
58.5g/mol)dissolved in 125 mL of solution. 
10 
M = molarity = moles of solutes 
volume of solution (L) 
mol NaCl = 34.6 g NaCl x 1 mol NaCl 
58.5 g NaCl 
= 0.59 mol NaCl 
M = 0.59 mol NaCl 
125 x 10-3 L = 4.73 mol/L
Example (2): 
How many grams of HCl (molar mass = 36.5 g/mol) would 
be required to make 50.0 mL of a 2.7 M solution? 
11 
M = 
moles of HCl 
volume of solution (L) 
2.7 (mol/L) = moles of HCl 
50.0 x10-3 L 
moles of HCl = 2.7 (mol/L) x 50.0 x10-3 L = 0.135 mol HCl 
36.5 g HCl = 4.93 g HCl 
Mass of HCl = 0.135 mol HCl x 1 mol HCl
mol of NaCl =1.0 x 10-3g NaCl x 1 mol NaCl 
12 
Example(3): 
Typical blood serum is about 0.14 M. what volume of 
blood contain 1.0 mg NaCl (molar mass = 58.5 g/mol). 
0.14 mol/L = 
58.5 g NaCl= 1.71 x 10-5 mol NaCl 
1.71 x 10-5 mol NaCl 
volume of blood serum 
volume of blood serum (L) = 1.71 x 10-5 mol NaCl 
0.14 mol/L 
= 1.2 x 10-4 L solution = 0.12 ml solution 
Thus: 0.12 ml of blood contain 1.71x10-5 mol NaCl or 1.0mg NaCl
13 
Solution concentration is always given in term of the form of the 
solute before it dissolves and does not take into account any 
subsequent processes, such as the dissociation of salts. 
e.g.: 1.0 M NaCl, this mean that 1.0 mol (58.5g) solid NaCl dissolved 
in enough water to make 1.0 L solution; it does not mean that the 
solution contain 1.0 mol of NaCl units. 
Actually, the solution contains 1.0 mol Na+ ions and 1.0 mol Cl- ions. 
Example (4): 
What is the concentration of each ions in 0.5M CaCl2 solution: 
CaCl2(s) Ca+ 
(aq) + 2 Cl- 
(aq) 
H2O 
1 mol CaCl2 that dissolved, the solution contain 1 mol Ca+2 and 2 mol 
Cl- ions. Thus 0.5 M CaCl2 contain 0.5 M Ca+2 and 2 x 0.5 M Cl- or 1 
M Cl-
1 mol CaCl2 = 0.24 mol CaCl2 a) 
14 
Example (5): 
A 27 g of CaCl2 (molar mass = 111 g/mol) dissolved in 
500 ml solution. Calculate: a) concentration of CaCl2 
b) concentration of each ion 
mol of CaCl2 = 27 g CaCl2 x 
111 g CaCl2 
M (CaCl2) = 0.24 mol CaCl2 
b) 1 mol CaCl2 
500 x 10-3 L = 0.48 M CaCl2 
1 mol Ca+2 
2 mol Cl- 
0.48 mol CaCl2 
0.48 mol Ca+2 
2 x 0.48 mol Cl- = 0.96 mol Cl-
Example (6): 
A 45.6 g of Fe2(SO4)3 (molar mass = 400 g/mol) dissolved in 
475 ml solution. Calculate: a) concentration of Fe2(SO4)3 
15 
b) concentration of 
eaMch (iFoen 2(SO4)3) = (mass/molar mass) Fe2(SO4)3 
V (L) solution 
M (Fe2(SO4)3) = 45.6 g/(400g/mol) 
475 x 10-3 L 
= 0.24 M or mol/L 
0.24 (mol/L) Fe2(SO4)3 
2 x 0.24 M Fe+3 = 0.48 M Fe+3 
3 x 0.24 M SO4 
-2 = 0.72 M SO4 
-2 
a) 
b)
16 
The number of moles of solute present in a given volume 
of solution of known molarity can be calculated as follows: 
Molarity (mol/L)= mol of solute 
volume of solution (L) 
mol of solute = molarity (mol/L) x volume of solution (L) 
Example (7): 
Calculate the number of mol of Cl- ions in 1.75L of 1x10-3 M ZnCl2 
1x10-3 M ZnCl2 
1x10-3 M Zn+2 
2 x(1x10-3)M Cl- = 2 x 10-3 M Cl-mol 
of Cl- = 2 x 10-3 mol Cl- 
L 
x 1.75 L = 3.5 x10-3 mol Cl-
Preparing a Solution of Known Concentration 
A standard solution: is a solution whose concentration is accurately 
known. It can be prepared as follows. First, the solute is accurately 
weighed and transferred to volumetric flask as shown in the following 
figure. Next water is added to the flask, to dissove the solid. After all 
the solid has dissolved, more 
water is added to bring the 
level of solution exactly to 
the volume mark. 
17 17
Example (8): Describe how to make 100.0 mL of a 1.0 M K2Cr2O4 
(molar mass =246 g/mol) solution. 
mol of K2Cr2O4 = 1.0 mol K2Cr2O4 
18 
L 
x 100 x 10-3 L = 0.1 mol K2Cr2O4 
mass of K2Cr2O4 = 0.1 mol K2Cr2O4 x 
246g K2Cr2O4 =24.6 g K2Cr2O4 
1 mol K2Cr2O4 
Thus, to prepare 100 ml of 1.0 M K2Cr2O4, weigh out 24.6g K2Cr2O4 , 
add distilled water until the volume of solution = 100ml 
Example (9): Describe how to make 250. mL of an 2.0 M copper (II) 
sulfate dihydrate (CuSO4.2H2O, molar mass = 200g/mol) solution. 
mol of CuSO4 = 2.0 mol CuSO4 x 250 x 10-3 L = 0.5 mol CuSO4 L 
mass of CuSO4 = 0.5 mol CuSO4 200 g CuSO4 
1 mol CuSO4 
= 100 g CuSO4 
Thus, to prepare 250.0 ml of 2.0 M CuSO4.2H2O, weigh out 100 g 
CuSO4.2H2O , add distilled water until the volume of solution = 250 ml
19 
Dilution 
 In the lab. a concentrated solutions are present, these solutions are 
called Stock solution. 
 Water is added to these solutions to achieve the molarity desired 
for a particular solution. 
 This process is called dilution: the procedure for preparing a less 
concentrated solution from more concentrated one 
 The moles of solute stay the same. 
Dilution 
Add Solvent 
Moles of solute 
before dilution (i) 
Moles of solute 
after dilution (f) 
= 
MiVi = MfVf
20 
Example: 
You have a 4.0 M stock solution. Describe how to make 1.0L of a 
0.75 M solution from the stock solution. 
(M V)conc. = (M V)dil. 
0.4 M x V = 0.75 M x 1.0 L 
Vconc. = 0.75 M x 1.0 L/ 4 M = 0.1875 L = 187.5 ml 
Take 187.5 ml of the stock solution, add water until the volume of 
the solution (solute and solute) become 1.0 L 
Example: 
18.5 mL of 2.3 M HCl is diluted to 250 mL with water. What is the 
concentration of the solution? 
M1 V1 = M2 V2 2.3 M x 18.5 ml = M2 x 250 ml 
M2 = 2.3 M x 18.5 ml / 250 ml 
M2 = 0.17 M
Example: 
A solution is prepared by dissolving 10.8 g of (NH4)2SO4 
(molar mass = 132 g/mol) in enough water to make 100 ml 
stock solution. A 10.0 ml of this stock solution is added to 
water to make 50.0 ml solution. Calculated the 
concentration of NH4 
21 
+ and SO4 
-2 ions in the final solution. 
moles of (NH4)2SO4 = 10.8 g 
132 g /mol = 0.0818 moles of (NH4)2SO4 
molarity of (NH4)2SO4 = 0.818 moles 
100 x 10-3 L 
= 0.818 M (NH4)2SO4 
(M V) conc. = (M V) dil. 
0.818 M x 10.0 ml = M x 50 ml 
M dil. = 0.16 M of (NH4)2SO4 
0.16 M of (NH4)2SO4 
0.16M SO4 
-2 
2 x 0.16M NH4 
+
22 
Classes of Reactions 
CChheemmiiccaall rreeaaccttiioonnss 
Precipitation 
reactions 
Acid-Base 
Reactions 
Oxidation-Reduction 
Reactions
23 
1) Precipitation reactions: 
 Occur in aqueous solutions of ionic compounds which results in 
the formation of an insoluble product, or a precipitate. 
 A precipitate is an insoluble solid that separates from the solution. 
 For example: Pb(NO3)2(aq) + 2 KI(aq) → PbI2(s) + KNO3(aq) 
 This reaction is an example of a metathesis reaction (also called 
double-displacement reaction): a reaction that involves the 
exchange of parts between the two compounds.
24 
Pb(NO3)2(s) Pb(NO3)2(aq) 
Pb2+ 
Ions in Aqueous Solution 
NO3 
1– 
NO3 
1– 
Na1+ I1– 
Pb2+(aq) + 2 NO3 
1–(aq) 
add 
water 
NaI(s) 
+ H2O(ℓ) 
dissociation: 
+ H2O(ℓ) 
Pb2+ 
NaI(aq) 
NO3 
1– 
NO3 
1– 
Na1+(aq) + I1–(aq) 
Mix them and get… 
Balance to get overall ionic equation… 
Cancel spectator ions to get net ionic equation… 
in solution 
Na1+ I1–
25 
Mix them and get… 
Pb(NO3)2(aq) + 2 NaI(aq) PbI2(s) + 2 NO3 
NO3 
Balance to get overall ionic equation… 
Pb2+(aq) + 2 NO3 
1–(aq) + 2 Na1+(aq) 
1–(aq) + 2 Na1+(aq) + 2 I1–(aq) PbI2(s) + 2 NO3 
1–(aq) + 2 Na1+(aq) 
Cancel spectator ions to get net ionic equation… 
Pb2+(aq) + 2 I1–(aq) PbI2(s) 
solid 
in solution 
Pb2+ 
NO3 
1– 
Na1+ I1– 
1– 
Na1+ I1– 
Pb2+ 
NO3 
1– 
Na1+ 
I1– 
NO3 
1– 
Na1+ 
I1–
26 
Mix together Zn(NO3)2(aq) and Ba(OH)2(aq): 
Ba(NO3)2 and (aq) Zn(OH)2 (ppt) 
Zn(NO3)2(aq) + Ba(OH)2(aq) Zn(OH)2(s) + 2 NO3 
Ba(OH)2(aq) 
Ba2+ 
OH1– 
OH1– 
NO3 
1– 
NO3 
1– 
Zn2+ 
(aq) + 2 NO3 
1– 
(aq) Ba2+ 
(aq) + 2 OH1– 
(aq) 
Zn(NO3)2(aq) 
Zn2+ 
Balance to get overall ionic equation… 
1– 
(aq) + Ba2+ 
(aq) 
Zn2+ 
(aq) + 2 NO3 
1– 
(aq) + Ba2+ 
(aq) + 2OH1– 
(aq) Zn(OH)2(s) + 2 NO3 
1– 
(aq) + Ba2+ 
(aq) 
Mix them and get… 
Cancel spectator ions to get net ionic equation… 
Zn2+ 
(aq) + 2 OH1– 
(aq) Zn(OH)2(s)
27 
Three Types of Equations 
 Molecular Equation- written as whole formulas, not the ions. 
K2CrO4(aq) + Ba(NO3)2(aq) → BaCrO4(s) + 2KNO3(aq) 
 Complete Ionic equation show dissolved electrolytes as the ions. 
2K+ 
(aq) + CrO4 
-2 
(aq) + Ba+2 
(aq) + 2 NO3 
- 
(aq) → 
BaCrO4(s) + 2K+ 
(aq) + 2 NO3 
- 
(aq) 
 Spectator ions are those that don’t react. 
 Net Ionic equations show only those ions that react, not the 
spectator ions 
Ba+2 
(aq) 
+ CrO4 
-2 
(aq) → BaCrO4(s)
How can we predict whether a precipitate will form or not when 
two aqueous solutions are mixed? It depends on the solubility of 
the solute. 
 The solubility is the maximum amount of solute that will dissolve 
in a given quantity of solvent at specific temperature. 
 Substances can be classified as soluble, slightly soluble, or 
insoluble 
 All ionic compounds are strong electrolytes, but they are not 
equally soluble 
 the solubility rules for common ionic compounds in water are as 
follows: 
28
29 
Solubility Rules 
1. Most nitrates (NO3 
-) are soluble. 
2. Most salts containing Group (I) ion and ammonium ion, 
NH4 
+, are soluble. 
3. Most chloride (Cl-), bromide (Br-), and iodide (I-) salts are 
soluble, except Ag+, Pb2+ and Hg2 
2+. 
4. Most sulfate (SO4 
-2) salts are soluble, except BaSO4, PbSO4, 
Hg2SO4, Ag2SO4 and CaSO4. 
5. Most hydroxides (OH-) except Group (1) and Ba(OH)2. 
6. Most sulfides (S-2), carbonates (CO3 
-2), chromates (CrO4 
-2), and 
phosphates (PO4 
-3)are only slightly soluble.
Examples: 
Predict if a precipitate is formed when the following 
solutions are mixed. Write the three types of equations for 
the reactions that lead to the formation of a precipitate. 
 iron (III) sulfate and potassium sulfide 
 Lead (II) nitrate and sulfuric acid. 
 NH4Cl(aq) + NaNO3(aq) → 
 AgNO3(aq) + KCl(aq) → 
 Zn(NO3)2(aq) + BaCr2O7(aq) → 
 CdCl2(aq) + Na2S(aq) → 
 NaOH(aq) + FeCl3(aq) → 
30
31 
Stoichiometry of Precipitation Reactions 
The procedure for doing stoichiometric calculations for 
solutions reactions are very similar to those for other 
types of reactions. 
The following steps are used: 
 Write the balanced net ionic equation for the reaction 
 Calculate the moles of the reactants. 
 Determine which reactant is limiting. 
 Calculate the moles of product or products, as 
required. 
 Convert to grams, as required
32 
Example (1) 
What mass of Na2CrO4 (molar mass = 162 g/mol) is 
required to precipitate all Ag+ ions from 75.0ml of 0.1 M 
solution AgNO3. 
2 AgNO3(aq) + Na2CrO4(s) → Ag2CrO4(s) + NaNO3(aq) 
Net ionic equation: 2Ag+ 
(aq)+ Na2CrO4(s)→Ag2CrO4(s) + 2Na+ 
(aq) 
moles of Ag+ = M x V = 0.1 (mol/L) x 75.0 x 10-3 L = 7.5 x 10-3 mol 
mol of Na2CrO4 = 7.5 x 10-3 mol Ag+ x 1 mol of Na2CrO4 
2 mol Ag+ 
= 3.8 x 10-3 mol Na2CrO4 
mass of Na2CrO4 = 3.8 x 10-3 mol Na2CrO4 x 162 g/mol 
= 0.616 g Na2CrO4
Example (2): 
Calculate the mass of Ba(OH)2 (molar mass = 171g/mol ) is 
formed when 100.00 mL of 0.100 M BaCl2 is mixed with 
100.00 mL of 0.100 M NaOH. 
BaCl2(aq) + 2 NaOH(aq) → Ba(OH)2(s) + 2 NaCl(aq) 
mol of of BaCl2 = M x V = 0.1(mol/L) x 100 x 10-3 L 
33 
= 0.01 mol 
mol of NaOH = 0.1(mol/L) x 100 x 10-3 L = 0.01 mol NaOH 
BaCl2 : 2 NaOH 
0.01 0.01/2 
NaOH is the limiting reactant 
mol of Ba(OH)2 = 0.01 mol NaOH x 1 mol Ba(OH)2 
2 mol NaOH 
= 0.005 mol Ba(OH)2 
mass Ba(OH)2 = 0.005 mol Ba(OH)2 x 
171 g Ba(OH)2 
1 mol Ba(OH)2 
= 0.855 g Ba(OH)2
Example (3): 
What volume of 0.204 M HCl is needed to precipitate all the 
silver ions from 50.ml of 0.0500 M silver nitrate solution. 
34 
AgNO3(aq) + HCl(aq) → AgCl(s) + 
mol of AgNO3 = M x V = 0.05 M x 50 x 10-3 L = 2.5 x 10-3 mol 
1 mol HCl = 2.5 x 10-3 mol 
mol of HCl = 2.5 x 10-3 mol AgNO3 x 1 mol AgNO3 
Molarity of HCl = mol of HCl 
Volume (L) 
Volume (L) =mol of HCl 
molarity of HCl 
volume of HCl = 2.5 x 10-3 mol 
0.204 mol/L = 0.01225 L = 12.23 ml
35 
2) Acid-Base reactions 
Arrhenius’s concept of acids and bases: 
Acid: is a substance that produce H+ ions when dissolved in 
water. 
Base: is a substance that produce OH- ions. 
A more general definition of a base (which include 
substances that do not contain OH-) was provided by 
Brǿnsted-Lowry whose defined acids and bases as 
follows: 
an acid is a proton donor. 
a base is a proton acceptor.
36 
When aqueous solution of HCl (strong electrolyte) is mixed with 
aqueous solution of NaOH(strong electrolyte), the reaction can be 
represented as follows: 
Molecular equation: HCl(aq) + NaOH(aq)→ NaCl(aq) + H2O(ℓ) 
Ionic equation : 
H+ 
(aq) + Cl- 
(aq) + Na+ 
(aq) + OH- 
(aq) → Na+ 
(aq) + Cl- 
(aq)+ H2O(ℓ) 
Net ionic equation: H+ 
(aq) + OH- 
(aq) → H2O(ℓ) 
So, all acid-base reaction can be represented as : 
Acid + Base → salt + water 
Acid - Base Reaction is often called a neutralization reaction. When 
enough acid is added to react exactly with the base, we say that the 
acid has been neutralized.
When aqueous solution of weak acid such as HCN is mixed with 
aqueous solution of NaOH, the reaction can be represented as 
follows: 
Molecular equation: HCN(aq) + NaOH(aq)→ NaCN(aq) + H2O(ℓ) 
Ionic equation : 
HCN 
37 
(aq) + Na+ 
(aq) + OH- 
(aq) → Na+ 
(aq) + CN- 
(aq)+ H2O(ℓ) 
Net ionic equation: HCN 
(aq) + OH- 
(aq) → CN- 
(aq) + H2O(ℓ) 
Note that only Na+ is a spectator ion. 
Example: write the ionic, and the net ionic equation for the following acid-base 
reaction: 
Na2CO3(aq) + 2 HCl → 2 NaCl(aq) + H2CO3(aq) 
H2CO3(aq) decompose as follows:H2CO3(aq) → CO2(g) + H2O(ℓ) 
Ionic equation: 
2 Na+ 
(aq) + CO-3 
(aq) + H+ 
(aq) + Cl- 
(aq) → CO2(g) + H2O(ℓ) +2 Na+ 
(aq) + 2 Cl- 
(aq) 
Net ionic equation: CO-3 
(aq) + H+ 
(aq) → CO2(g) + H2O(ℓ)
Acid-Base Titration: 
Quantitative studies of acid-base neutralization reactions are carried 
out using a technique known as titration. 
In titration, a solution of accurately known concentration (standard 
solution) is added gradually by using the buret to another solution 
of unknown concentration, until the chemical reaction between the 
two solutions is complete. The reaction is said to be complete when 
we reach the Equivalence point. 
Equivalence point – the point at which the reaction is complete 
The equivalence point is usually 
signaled by a sharp change in the 
Color of an indicator 
Indicator – substance that changes 
color at (or near) the equivalence point 
38
Example (1): 
75 mL of 0.25M HCl is mixed with 225 mL of 0.055 M 
Ba(OH)2 . calculate : a) the amount of H2O produce. 
39 
b) the concentration of the excess H+ or OH-Ba( 
OH)2(aq) + 2HCl(aq) → BaCl2(aq) + 2 H2O(ℓ) 
moles of HCl = 0.25 M x 75x10-3L = 0.01875 mol 
mol of Ba(OH)= 0.055 M x 225x10-3L = 0.012375 mol 
2 Ba(OH): 2 HCl 
2 0.012375 : 0.01875/2 2 mol limiting HO reactant 2x 18 g His HCl 
O 
2Mass of HO = 0.01875 mol HCl x 2 mol HCl 
1 mol HO 
22= 0.3375 g H2O
40 
b) moles of Ba(OH)2 reacted = 0.01875 mol HCl x 
1 mol Ba(OH)2 
2 mol HCl 
= 0.009375 mol Ba(OH)2 
Total mol of Ba(OH)2 = mol Ba(OH)2reacted + mol Ba(OH)2 unreacted 
0.012375 mol = 0.009375 mol + mol Ba(OH)2unreacted 
mol Ba(OH)2 unreacted = 0.003 mol 
mol of OH- = 2 x 0.003 mol = 0.006 mol 
Molarity of OH- = 0.006 mol OH-total 
volume (L) 
= 0.006 mol 
300 x 10-3 L 
= 0.02 M OH-
Example (2): 
A 50.00 mL sample of aqueous Ca(OH)2 requires 34.66 mL 
of 0.0980 M HNO3 for neutralization. What is the 
concentration of Ca(OH)2. 
Ca(OH)2(aq) + 2HNO3(aq) → Ca(NO3)2(aq) + 2H2O(ℓ) 
mol of HNO3 = 0.098 (mol/L) x 34.66x10-3 L = 3.4 x10-3 mol 
mol of Ca(OH)2 = 3.4 x 10-3 mol HNO3 x 2 mol HNO3 
41 
1 mol Ca(OH)2 
= 1.7 x 10-3 mol Ca(OH)2 
molarity of Ca(OH)2= 1.7 x 10-3 mol 
50 x 10-3 L 
= 0.034 M
3) Oxidation-Reduction (called Redox) Reactions: 
For the following reaction: 
2 Na(s) + Cl2(g) → 2 NaCl(s) 
Na is a neutral atom react with Cl2 which is also a neutral 
compound to form NaCl which contain Na+ and Cl- ions. 
Reactions like this one, which involves the transfer of 
electrons, are called oxidation-reduction (or redox) 
reactions. 
Many important redox reactions occur in our daily life, e.g.: 
Photosynthesis, combustion of sugar in our body,..etc. 
To explain how electrons are transfer, the concept of 
oxidation states must be introduced. 
42
43 
Oxidation States 
The concept of oxidation states (or oxidation numbers) 
provides a way of keeping track of the electrons in oxidation 
reduction reactions. 
 need the rules for assigning oxidation states (memorize). 
 The sum of the oxidation states must be zero in 
compounds or equal the charge of the ion. 
 The following table summarized the rules for assigning the 
oxidation states
44 
…The oxidation state of summary examples 
• elements in their standard 
states is zero 
Element: 0 Na(s), O2(g) , Hg(ℓ) 
•monoatomic ions are the same 
as their charge. 
Monoatomic ions: 
Charge of ion 
Na+ , Cl-, Ca+2 
•Oxygen is assigned an 
oxidation state of -2 in its 
covalent compounds except as a 
peroxide (O2 
-2, oxygen is -1, e.g. 
H2O2) 
Oxygen : -2 
H2O , CO2 , CO 
•hydrogen is assigned the 
oxidation state +1, except when 
it bonded to metals; LiH, NaH 
…, its oxidation state is -1 
Hydrogen: +1 HCN, HCl, NH3 
•fluorine is always –1 in its 
compounds. 
Flourine: -1 HF, PF3
The following figure shows oxidation numbers of familiar elements, 
arranged according to their position in the periodic table. 
45
Example: 
Assign the oxidation states to each element in the following 
compounds. 
 CO2 : O is -2, so -2 x 2 + C = 0 C = +4 
 NO3 
46 
- : O is -2, so (3 x -2)+ N = -1 N = +5 
 H2SO4 : H is +1, O is -2, so [2x(+1)]+[(4x(-2)]+S =0 
S = +6 
 FeO: O is -2, so [3x(-2)]+ 2xFe = 0 Fe = +3 
23  CrO-2 : 2xCr +[7x(-2)]= -2 Cr = +6 
27
Oxidation-reduction reactions are characterized by the 
transfer electrons, so the oxidation states change. 
For the following reactions: 
1) 2 Na + Cl2 → 2NaCl 
Oxidation 
state 0 0 +1 -1 
47 
2) CH4 + 2O2 → CO2 + 2H2O 
Oxidation 
state -4 +1 
(each H) 0 
+4 -2 
(each O) +1 
each H 
-2 
Carbon undergoes a change in oxidation state from -4 in CH4 
to +4 in CO2, 8 electrons (symbol e- stands for electrons) are 
lost
48 
CH4 → CO2 + 8 e- 
-4 +4 
Each oxygen change from an oxidation state 0 in O2 to -2 
in H2O and CO2 , each atom gain 2 electrons. Since four 
oxygen atoms are involved , this is a gain of 8 electrons. 
O2 + 8 e- → CO2 + 2 H2O 
0 4 x (-2)= - 8 
No change occurs in the oxidation state of hydrogen .
We can now define some important terms: 
 Oxidation is the loss of electrons or an increase in 
oxidation state - lose electrons. . 
 Reduction is the gain of electrons or a decrease in 
oxidation state - gain electrons. 
 The substance that is oxidized is called the reducing agent. 
Reducing agent gets oxidized. Loses electrons. 
More positive oxidation state. 
 The substance that is reduced is called the oxidizing agent. 
Oxidizing agent gets reduced. Gains electrons. More 
negative oxidation state. 
49
50 
Example: 
For the following reactions, identify 
 Substance oxidized 
 Substance reduced 
 Oxidizing agent 
 Reducing agent 
1) Fe (s) + O2(g) → Fe2O3(s) 
0 0 + 3 -2 
The oxidation state for Fe increase from 0 to +3. thus Fe is oxidized. 
The oxidation state for O decrease from 0 to -2. thus O is reduced. 
The oxidizing agent is O2. 
The reducing agent is Fe.
+3 -2 +2 -2 0 +4 -2 
The oxidation state for C increase from +2 to +4. thus C is oxidized. 
The oxidation state for Fe decrease from +3 to 0. thus O is reduced. 
The oxidizing agent is Fe. 
The reducing agent is CO. 
51 
2) Fe2O3(s) + 3 CO(g) → 2 Fe(s) + 3 CO2(g) 
3) SO3 
2- + H+ + MnO4 
- → SO4 
2- + H2O + Mn2+ 
+4 -2 +1 +7 -2 +6 -2 +1 -2 +2 
The oxidation state for S increase from +4 to +6. thus S is oxidized. 
The oxidation state for Mn decrease from +7 to +2. thus Mn is reduced. 
The oxidizing agent is MnO-. 
4 
The reducing agent is SO3 
2-.
52 
Balancing oxidation-reduction equations 
It is difficult to balance redox equations by simple 
inspection, the technique used for balancing redox reactions 
called the half-reaction method. 
 All redox reactions can be thought of as happening in two 
halves. 
 One produces electrons - Oxidation half. 
 The other requires electrons - Reduction half. 
 Write the half reactions for the following. 
1) Na + Cl2 → Na+ + Cl- 
2) Ce+4 + Sn+2 → Ce+3 + Sn+4
53 
1) Na + Cl2 → Na+ + Cl- 
Na → Na+ oxidation 
Cl2 → Cl- reduction 
2) Ce+4 + Sn+2 → Ce+3 + Sn+4 
Ce+4 → Ce+3 reduction 
Sn+2 → Sn+4 oxidation 
The method for balancing redox equations differ slightly 
depending on whether the reaction takes place in acidic or 
basic solution.
Balancing Redox Equations in acidic solution 
 In aqueous solutions the key is the number of electrons 
produced must be the same as those required. 
 For reactions in acidic solution an 8 step procedure. 
1.Write separate equations for the oxidation-reduction half reactions 
2. For each half reaction balance all reactants except H and O 
3. Balance O using H2O 
4. Balance H using H+ 
5. Balance charge using e- 
6. Multiply equations to make electrons equal 
7. Add the half-reactions, and cancel identical species 
8 Check that charges and elements are balanced. 
54
55 
Examples: 
Balance the following oxidation-reduction reactions occur 
in acidic aqueous solution. 
1) MnO- + Fe+2 → Mn+2 + Fe+3 
4 
1) Write the half reactions 
MnO4 
- → Mn+2 Fe+2 → Fe+3 
2) Balance each half-reaction: 
MnO4 
- → Mn+2 
-Mn is balanced 
-balance oxygen by adding 4H2O to the write side of the equation. 
- Balance hydrogen by adding 8H+ to the left side of equation. 
8H+ + MnO4 
- → Mn+2 + 4H2O
56 
-Balance the charge using electrons 
8H+ + MnO4 
- → Mn+2 + 4H2O 
+8 -1 → +2 0 
+7 +2 
equalize the charges by adding five electrons to the left side. 
5e- + 8H+ + MnO4 
- → Mn+2 + 4H2O reduction 
+2 +2 
both the elements and charges are now balanced. 
For the oxidation reaction: Fe+2 → Fe+3 + e- 
+2 +3-1 
+2 +2
Equalize the electron transfer in the two half-reactions 
57 
5e- + 8H+ + MnO4 
- → Mn+2 + 4H2O 
5 Fe+2 → 5 Fe+3 + 5e- 
8H+ + MnO4 
- + 5 Fe+2 → Mn+2 + 4H2O + 5 Fe+3 
check that elements and charges are balanced. 
elements balance: 5Fe, 1Mn, 4O, 8H→ 5Fe, 1Mn, 4O, 8H 
charge balance: 8(+1)+(-1)+5(+2)→(+2)+0+5(+3) 
+17 → +17 
the equation is balanced.
58 
2) Cu + NO3 
- → Cu+2 + NO(g) 
3 / Cu → Cu+2 + 2e- 
2 / 3e- + 4H+ + NO3 
- → NO + 2H2O 
3Cu + 8H+ + 2NO3 
- → 3Cu+2 + 2NO + 4H2O 
3) Mn+2 + BiO3 
- → Bi+3 + MnO4 
- 
2 / 4 H2O + Mn+2 → MnO4 
- + 8H+ +5e- 
+2 +7 
5/ 2e- + 6H+ +BiO3 
- → Bi+3 + 3H2O 
+5 +3 
2Mn+2 + 5BiO3 
- + 14H+ → 2MnO4 
- + 5Bi+3 + 7H2O
Balancing Redox Equations in basic solution 
 Do everything you would with acid, but add one more 
step. 
 Add enough OH- to both sides to neutralize the H+ 
 Makes water 
Examples: 
Balance the following equation in basic solutions: 
59 
Cr(OH)3 + OCl- + OH- → CrO4 
2- + Cl- + H2O
Cr(OH)3 + OCl- + OH- → CrO4 
60 
2- + Cl- + H2O 
2/ Cr(OH)3 + H2O → CrO4 
2- + 5H++3e- 
0 +3 
3/ 2e- + OCl- + 2H+ → Cl- + H2O 
+1 -1 
2- + 3Cl- +H2O +4H+ (acidic solution) 
2Cr(OH)3 + 3OCl- → 2CrO4 
4OH- +2Cr(OH)3 + 3OCl- → 2CrO4 
2- + 3Cl- +H2O + 4H+ + 4OH- 
4OH- +2Cr(OH)3 + 3OCl- → 2CrO4 
2- + 3Cl- +5H2O (basic solution)
Example: 16.42 mL of 0.1327 M KMnO4 solution is needed to 
oxidize 25.00 mL of an acidic FeSO4 solution. What is the molarity of 
the iron solution: 
5Fe2+ + MnO4 
- + 8H+ Mn2+ + 5Fe3+ + 4H2O 
0.01642 L 0.1327 mol KMnOx 
4 
1 L 
x 
5 mol Fe2+ 
1 mol KMnO4 
x 
1 
0.02500 L Fe2+ 
= 0.4358 M Fe2+ 
61 61

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Understanding Aqueous Chemistry

  • 2. 2 Many chemical reactions and virtually all biological processes take place in water. e.g.: all chemistry that makes life possible occur in aqueous solution, various medical tests involve aqueous reactions like sugar tests..cholesterol .. ect To understand the chemistry that occur in such diverse places as human body, the atmosphere, the ground water, the oceans, and so on, we must understand how substances dissolved in water react with each other.
  • 3. 3 Before we can understand solution reactions, we need to discuss the nature of solutions in which water is the dissolving medium or solvent. These solutions- (homogeneous mixture) are called aqueous solutions. aqueous solutions Solvent Solute what gets Soluble- Can be dissolved. Miscible- liquids dissolve in each other. dissolved what does the dissolving
  • 4. 4 Water, the common solvent One of the most valuable properties of water is ability to dissolve many different substances. Water is a good solvent for ionic compounds because its molecules are polar. The oxygen atoms have a partial negative charge. The hydrogen atoms have a partial positive charge. The angle is 104.5ºC. It is the polarity that gives water its great ability to dissolve compounds + δ + δ -δ
  • 5. 5 A schematic of an ionic solid dissolving in water is shown in the following figure. The “positive ends” of water molecules are attracted to the negatively charged anions and the “negative ends” are attracted to the positively charged cations This process is called hydration The hydration process is breaking the ionic substances (salts) apart into individual cations and anions and surrounded by water molecules When NaCl dissolves in water, the resulting solution contains Na+ and Cl- ions moving around independently. NaCl(s) Na+ (aq) + Cl- H (aq) 2O(ℓ)
  • 6. How Ionic solids dissolve H H O 6 O H H H H O O H H H H O H H O O H H H H O H O H
  • 7. 7 The solubility is how much of a substance will dissolve in a given amount of water, usually g/100 mL The solubility of ionic substances in water varies greatly, e.g: NaCl soluble in water, whereas AgCl insoluble in water If the ionic substance do dissolve the ions are separated, and they can move around. Water can also dissolve non-ionic compounds if they have polar bonds like ethanol (C2H5OH). “Like dissolve like” is a useful rule for predicting solubility.
  • 8. 8 Types of solutions Solutions are classified three ways Strong electrolytes- completely dissociate (fall apart into ions). - Many ions - Conduct electricity well. e.g.: NaCl give Na+ , Cl- when dissolve in water Weak electrolytes- Partially fall apart into ions. – Few ions -Conduct electricity slightly. e.g.: acetic acid dissociate partially in water. Non-electrolytes- Don’t fall apart. - No ions- Don’t conduct electricity. e.g.: sugar ( C12H22O12) , ethanol (C2H5OH)
  • 9. 9 The composition of solution Chemical reactions take place when two solution are mixed. To perform stoichiometric calculations in such cases, two things must be known: 1.The nature of the reaction 2.The amount of chemicals present in the solution, expressed as concentrations. Concentration: is how much solute is dissolved in a given amount of solvent. The concentration of solution can be expressed in many different ways. We will consider only the most commonly used expression of concentration, molarity
  • 10. Molarity (M): moles of solute per volume of solution in liters 1 M = 1 mol solute / 1 liter solution 1 M = 1 mol solute dissolved water until the volume of solute and solvent (solution) become 1 liter The concentration is an intensive property, so its value does not depend on how much of the solution is present. Example (1): Calculate the molarity of a solution with 34.6 g of NaCl (molar mass = 58.5g/mol)dissolved in 125 mL of solution. 10 M = molarity = moles of solutes volume of solution (L) mol NaCl = 34.6 g NaCl x 1 mol NaCl 58.5 g NaCl = 0.59 mol NaCl M = 0.59 mol NaCl 125 x 10-3 L = 4.73 mol/L
  • 11. Example (2): How many grams of HCl (molar mass = 36.5 g/mol) would be required to make 50.0 mL of a 2.7 M solution? 11 M = moles of HCl volume of solution (L) 2.7 (mol/L) = moles of HCl 50.0 x10-3 L moles of HCl = 2.7 (mol/L) x 50.0 x10-3 L = 0.135 mol HCl 36.5 g HCl = 4.93 g HCl Mass of HCl = 0.135 mol HCl x 1 mol HCl
  • 12. mol of NaCl =1.0 x 10-3g NaCl x 1 mol NaCl 12 Example(3): Typical blood serum is about 0.14 M. what volume of blood contain 1.0 mg NaCl (molar mass = 58.5 g/mol). 0.14 mol/L = 58.5 g NaCl= 1.71 x 10-5 mol NaCl 1.71 x 10-5 mol NaCl volume of blood serum volume of blood serum (L) = 1.71 x 10-5 mol NaCl 0.14 mol/L = 1.2 x 10-4 L solution = 0.12 ml solution Thus: 0.12 ml of blood contain 1.71x10-5 mol NaCl or 1.0mg NaCl
  • 13. 13 Solution concentration is always given in term of the form of the solute before it dissolves and does not take into account any subsequent processes, such as the dissociation of salts. e.g.: 1.0 M NaCl, this mean that 1.0 mol (58.5g) solid NaCl dissolved in enough water to make 1.0 L solution; it does not mean that the solution contain 1.0 mol of NaCl units. Actually, the solution contains 1.0 mol Na+ ions and 1.0 mol Cl- ions. Example (4): What is the concentration of each ions in 0.5M CaCl2 solution: CaCl2(s) Ca+ (aq) + 2 Cl- (aq) H2O 1 mol CaCl2 that dissolved, the solution contain 1 mol Ca+2 and 2 mol Cl- ions. Thus 0.5 M CaCl2 contain 0.5 M Ca+2 and 2 x 0.5 M Cl- or 1 M Cl-
  • 14. 1 mol CaCl2 = 0.24 mol CaCl2 a) 14 Example (5): A 27 g of CaCl2 (molar mass = 111 g/mol) dissolved in 500 ml solution. Calculate: a) concentration of CaCl2 b) concentration of each ion mol of CaCl2 = 27 g CaCl2 x 111 g CaCl2 M (CaCl2) = 0.24 mol CaCl2 b) 1 mol CaCl2 500 x 10-3 L = 0.48 M CaCl2 1 mol Ca+2 2 mol Cl- 0.48 mol CaCl2 0.48 mol Ca+2 2 x 0.48 mol Cl- = 0.96 mol Cl-
  • 15. Example (6): A 45.6 g of Fe2(SO4)3 (molar mass = 400 g/mol) dissolved in 475 ml solution. Calculate: a) concentration of Fe2(SO4)3 15 b) concentration of eaMch (iFoen 2(SO4)3) = (mass/molar mass) Fe2(SO4)3 V (L) solution M (Fe2(SO4)3) = 45.6 g/(400g/mol) 475 x 10-3 L = 0.24 M or mol/L 0.24 (mol/L) Fe2(SO4)3 2 x 0.24 M Fe+3 = 0.48 M Fe+3 3 x 0.24 M SO4 -2 = 0.72 M SO4 -2 a) b)
  • 16. 16 The number of moles of solute present in a given volume of solution of known molarity can be calculated as follows: Molarity (mol/L)= mol of solute volume of solution (L) mol of solute = molarity (mol/L) x volume of solution (L) Example (7): Calculate the number of mol of Cl- ions in 1.75L of 1x10-3 M ZnCl2 1x10-3 M ZnCl2 1x10-3 M Zn+2 2 x(1x10-3)M Cl- = 2 x 10-3 M Cl-mol of Cl- = 2 x 10-3 mol Cl- L x 1.75 L = 3.5 x10-3 mol Cl-
  • 17. Preparing a Solution of Known Concentration A standard solution: is a solution whose concentration is accurately known. It can be prepared as follows. First, the solute is accurately weighed and transferred to volumetric flask as shown in the following figure. Next water is added to the flask, to dissove the solid. After all the solid has dissolved, more water is added to bring the level of solution exactly to the volume mark. 17 17
  • 18. Example (8): Describe how to make 100.0 mL of a 1.0 M K2Cr2O4 (molar mass =246 g/mol) solution. mol of K2Cr2O4 = 1.0 mol K2Cr2O4 18 L x 100 x 10-3 L = 0.1 mol K2Cr2O4 mass of K2Cr2O4 = 0.1 mol K2Cr2O4 x 246g K2Cr2O4 =24.6 g K2Cr2O4 1 mol K2Cr2O4 Thus, to prepare 100 ml of 1.0 M K2Cr2O4, weigh out 24.6g K2Cr2O4 , add distilled water until the volume of solution = 100ml Example (9): Describe how to make 250. mL of an 2.0 M copper (II) sulfate dihydrate (CuSO4.2H2O, molar mass = 200g/mol) solution. mol of CuSO4 = 2.0 mol CuSO4 x 250 x 10-3 L = 0.5 mol CuSO4 L mass of CuSO4 = 0.5 mol CuSO4 200 g CuSO4 1 mol CuSO4 = 100 g CuSO4 Thus, to prepare 250.0 ml of 2.0 M CuSO4.2H2O, weigh out 100 g CuSO4.2H2O , add distilled water until the volume of solution = 250 ml
  • 19. 19 Dilution In the lab. a concentrated solutions are present, these solutions are called Stock solution. Water is added to these solutions to achieve the molarity desired for a particular solution. This process is called dilution: the procedure for preparing a less concentrated solution from more concentrated one The moles of solute stay the same. Dilution Add Solvent Moles of solute before dilution (i) Moles of solute after dilution (f) = MiVi = MfVf
  • 20. 20 Example: You have a 4.0 M stock solution. Describe how to make 1.0L of a 0.75 M solution from the stock solution. (M V)conc. = (M V)dil. 0.4 M x V = 0.75 M x 1.0 L Vconc. = 0.75 M x 1.0 L/ 4 M = 0.1875 L = 187.5 ml Take 187.5 ml of the stock solution, add water until the volume of the solution (solute and solute) become 1.0 L Example: 18.5 mL of 2.3 M HCl is diluted to 250 mL with water. What is the concentration of the solution? M1 V1 = M2 V2 2.3 M x 18.5 ml = M2 x 250 ml M2 = 2.3 M x 18.5 ml / 250 ml M2 = 0.17 M
  • 21. Example: A solution is prepared by dissolving 10.8 g of (NH4)2SO4 (molar mass = 132 g/mol) in enough water to make 100 ml stock solution. A 10.0 ml of this stock solution is added to water to make 50.0 ml solution. Calculated the concentration of NH4 21 + and SO4 -2 ions in the final solution. moles of (NH4)2SO4 = 10.8 g 132 g /mol = 0.0818 moles of (NH4)2SO4 molarity of (NH4)2SO4 = 0.818 moles 100 x 10-3 L = 0.818 M (NH4)2SO4 (M V) conc. = (M V) dil. 0.818 M x 10.0 ml = M x 50 ml M dil. = 0.16 M of (NH4)2SO4 0.16 M of (NH4)2SO4 0.16M SO4 -2 2 x 0.16M NH4 +
  • 22. 22 Classes of Reactions CChheemmiiccaall rreeaaccttiioonnss Precipitation reactions Acid-Base Reactions Oxidation-Reduction Reactions
  • 23. 23 1) Precipitation reactions: Occur in aqueous solutions of ionic compounds which results in the formation of an insoluble product, or a precipitate. A precipitate is an insoluble solid that separates from the solution. For example: Pb(NO3)2(aq) + 2 KI(aq) → PbI2(s) + KNO3(aq) This reaction is an example of a metathesis reaction (also called double-displacement reaction): a reaction that involves the exchange of parts between the two compounds.
  • 24. 24 Pb(NO3)2(s) Pb(NO3)2(aq) Pb2+ Ions in Aqueous Solution NO3 1– NO3 1– Na1+ I1– Pb2+(aq) + 2 NO3 1–(aq) add water NaI(s) + H2O(ℓ) dissociation: + H2O(ℓ) Pb2+ NaI(aq) NO3 1– NO3 1– Na1+(aq) + I1–(aq) Mix them and get… Balance to get overall ionic equation… Cancel spectator ions to get net ionic equation… in solution Na1+ I1–
  • 25. 25 Mix them and get… Pb(NO3)2(aq) + 2 NaI(aq) PbI2(s) + 2 NO3 NO3 Balance to get overall ionic equation… Pb2+(aq) + 2 NO3 1–(aq) + 2 Na1+(aq) 1–(aq) + 2 Na1+(aq) + 2 I1–(aq) PbI2(s) + 2 NO3 1–(aq) + 2 Na1+(aq) Cancel spectator ions to get net ionic equation… Pb2+(aq) + 2 I1–(aq) PbI2(s) solid in solution Pb2+ NO3 1– Na1+ I1– 1– Na1+ I1– Pb2+ NO3 1– Na1+ I1– NO3 1– Na1+ I1–
  • 26. 26 Mix together Zn(NO3)2(aq) and Ba(OH)2(aq): Ba(NO3)2 and (aq) Zn(OH)2 (ppt) Zn(NO3)2(aq) + Ba(OH)2(aq) Zn(OH)2(s) + 2 NO3 Ba(OH)2(aq) Ba2+ OH1– OH1– NO3 1– NO3 1– Zn2+ (aq) + 2 NO3 1– (aq) Ba2+ (aq) + 2 OH1– (aq) Zn(NO3)2(aq) Zn2+ Balance to get overall ionic equation… 1– (aq) + Ba2+ (aq) Zn2+ (aq) + 2 NO3 1– (aq) + Ba2+ (aq) + 2OH1– (aq) Zn(OH)2(s) + 2 NO3 1– (aq) + Ba2+ (aq) Mix them and get… Cancel spectator ions to get net ionic equation… Zn2+ (aq) + 2 OH1– (aq) Zn(OH)2(s)
  • 27. 27 Three Types of Equations Molecular Equation- written as whole formulas, not the ions. K2CrO4(aq) + Ba(NO3)2(aq) → BaCrO4(s) + 2KNO3(aq) Complete Ionic equation show dissolved electrolytes as the ions. 2K+ (aq) + CrO4 -2 (aq) + Ba+2 (aq) + 2 NO3 - (aq) → BaCrO4(s) + 2K+ (aq) + 2 NO3 - (aq) Spectator ions are those that don’t react. Net Ionic equations show only those ions that react, not the spectator ions Ba+2 (aq) + CrO4 -2 (aq) → BaCrO4(s)
  • 28. How can we predict whether a precipitate will form or not when two aqueous solutions are mixed? It depends on the solubility of the solute. The solubility is the maximum amount of solute that will dissolve in a given quantity of solvent at specific temperature. Substances can be classified as soluble, slightly soluble, or insoluble All ionic compounds are strong electrolytes, but they are not equally soluble the solubility rules for common ionic compounds in water are as follows: 28
  • 29. 29 Solubility Rules 1. Most nitrates (NO3 -) are soluble. 2. Most salts containing Group (I) ion and ammonium ion, NH4 +, are soluble. 3. Most chloride (Cl-), bromide (Br-), and iodide (I-) salts are soluble, except Ag+, Pb2+ and Hg2 2+. 4. Most sulfate (SO4 -2) salts are soluble, except BaSO4, PbSO4, Hg2SO4, Ag2SO4 and CaSO4. 5. Most hydroxides (OH-) except Group (1) and Ba(OH)2. 6. Most sulfides (S-2), carbonates (CO3 -2), chromates (CrO4 -2), and phosphates (PO4 -3)are only slightly soluble.
  • 30. Examples: Predict if a precipitate is formed when the following solutions are mixed. Write the three types of equations for the reactions that lead to the formation of a precipitate. iron (III) sulfate and potassium sulfide Lead (II) nitrate and sulfuric acid. NH4Cl(aq) + NaNO3(aq) → AgNO3(aq) + KCl(aq) → Zn(NO3)2(aq) + BaCr2O7(aq) → CdCl2(aq) + Na2S(aq) → NaOH(aq) + FeCl3(aq) → 30
  • 31. 31 Stoichiometry of Precipitation Reactions The procedure for doing stoichiometric calculations for solutions reactions are very similar to those for other types of reactions. The following steps are used: Write the balanced net ionic equation for the reaction Calculate the moles of the reactants. Determine which reactant is limiting. Calculate the moles of product or products, as required. Convert to grams, as required
  • 32. 32 Example (1) What mass of Na2CrO4 (molar mass = 162 g/mol) is required to precipitate all Ag+ ions from 75.0ml of 0.1 M solution AgNO3. 2 AgNO3(aq) + Na2CrO4(s) → Ag2CrO4(s) + NaNO3(aq) Net ionic equation: 2Ag+ (aq)+ Na2CrO4(s)→Ag2CrO4(s) + 2Na+ (aq) moles of Ag+ = M x V = 0.1 (mol/L) x 75.0 x 10-3 L = 7.5 x 10-3 mol mol of Na2CrO4 = 7.5 x 10-3 mol Ag+ x 1 mol of Na2CrO4 2 mol Ag+ = 3.8 x 10-3 mol Na2CrO4 mass of Na2CrO4 = 3.8 x 10-3 mol Na2CrO4 x 162 g/mol = 0.616 g Na2CrO4
  • 33. Example (2): Calculate the mass of Ba(OH)2 (molar mass = 171g/mol ) is formed when 100.00 mL of 0.100 M BaCl2 is mixed with 100.00 mL of 0.100 M NaOH. BaCl2(aq) + 2 NaOH(aq) → Ba(OH)2(s) + 2 NaCl(aq) mol of of BaCl2 = M x V = 0.1(mol/L) x 100 x 10-3 L 33 = 0.01 mol mol of NaOH = 0.1(mol/L) x 100 x 10-3 L = 0.01 mol NaOH BaCl2 : 2 NaOH 0.01 0.01/2 NaOH is the limiting reactant mol of Ba(OH)2 = 0.01 mol NaOH x 1 mol Ba(OH)2 2 mol NaOH = 0.005 mol Ba(OH)2 mass Ba(OH)2 = 0.005 mol Ba(OH)2 x 171 g Ba(OH)2 1 mol Ba(OH)2 = 0.855 g Ba(OH)2
  • 34. Example (3): What volume of 0.204 M HCl is needed to precipitate all the silver ions from 50.ml of 0.0500 M silver nitrate solution. 34 AgNO3(aq) + HCl(aq) → AgCl(s) + mol of AgNO3 = M x V = 0.05 M x 50 x 10-3 L = 2.5 x 10-3 mol 1 mol HCl = 2.5 x 10-3 mol mol of HCl = 2.5 x 10-3 mol AgNO3 x 1 mol AgNO3 Molarity of HCl = mol of HCl Volume (L) Volume (L) =mol of HCl molarity of HCl volume of HCl = 2.5 x 10-3 mol 0.204 mol/L = 0.01225 L = 12.23 ml
  • 35. 35 2) Acid-Base reactions Arrhenius’s concept of acids and bases: Acid: is a substance that produce H+ ions when dissolved in water. Base: is a substance that produce OH- ions. A more general definition of a base (which include substances that do not contain OH-) was provided by Brǿnsted-Lowry whose defined acids and bases as follows: an acid is a proton donor. a base is a proton acceptor.
  • 36. 36 When aqueous solution of HCl (strong electrolyte) is mixed with aqueous solution of NaOH(strong electrolyte), the reaction can be represented as follows: Molecular equation: HCl(aq) + NaOH(aq)→ NaCl(aq) + H2O(ℓ) Ionic equation : H+ (aq) + Cl- (aq) + Na+ (aq) + OH- (aq) → Na+ (aq) + Cl- (aq)+ H2O(ℓ) Net ionic equation: H+ (aq) + OH- (aq) → H2O(ℓ) So, all acid-base reaction can be represented as : Acid + Base → salt + water Acid - Base Reaction is often called a neutralization reaction. When enough acid is added to react exactly with the base, we say that the acid has been neutralized.
  • 37. When aqueous solution of weak acid such as HCN is mixed with aqueous solution of NaOH, the reaction can be represented as follows: Molecular equation: HCN(aq) + NaOH(aq)→ NaCN(aq) + H2O(ℓ) Ionic equation : HCN 37 (aq) + Na+ (aq) + OH- (aq) → Na+ (aq) + CN- (aq)+ H2O(ℓ) Net ionic equation: HCN (aq) + OH- (aq) → CN- (aq) + H2O(ℓ) Note that only Na+ is a spectator ion. Example: write the ionic, and the net ionic equation for the following acid-base reaction: Na2CO3(aq) + 2 HCl → 2 NaCl(aq) + H2CO3(aq) H2CO3(aq) decompose as follows:H2CO3(aq) → CO2(g) + H2O(ℓ) Ionic equation: 2 Na+ (aq) + CO-3 (aq) + H+ (aq) + Cl- (aq) → CO2(g) + H2O(ℓ) +2 Na+ (aq) + 2 Cl- (aq) Net ionic equation: CO-3 (aq) + H+ (aq) → CO2(g) + H2O(ℓ)
  • 38. Acid-Base Titration: Quantitative studies of acid-base neutralization reactions are carried out using a technique known as titration. In titration, a solution of accurately known concentration (standard solution) is added gradually by using the buret to another solution of unknown concentration, until the chemical reaction between the two solutions is complete. The reaction is said to be complete when we reach the Equivalence point. Equivalence point – the point at which the reaction is complete The equivalence point is usually signaled by a sharp change in the Color of an indicator Indicator – substance that changes color at (or near) the equivalence point 38
  • 39. Example (1): 75 mL of 0.25M HCl is mixed with 225 mL of 0.055 M Ba(OH)2 . calculate : a) the amount of H2O produce. 39 b) the concentration of the excess H+ or OH-Ba( OH)2(aq) + 2HCl(aq) → BaCl2(aq) + 2 H2O(ℓ) moles of HCl = 0.25 M x 75x10-3L = 0.01875 mol mol of Ba(OH)= 0.055 M x 225x10-3L = 0.012375 mol 2 Ba(OH): 2 HCl 2 0.012375 : 0.01875/2 2 mol limiting HO reactant 2x 18 g His HCl O 2Mass of HO = 0.01875 mol HCl x 2 mol HCl 1 mol HO 22= 0.3375 g H2O
  • 40. 40 b) moles of Ba(OH)2 reacted = 0.01875 mol HCl x 1 mol Ba(OH)2 2 mol HCl = 0.009375 mol Ba(OH)2 Total mol of Ba(OH)2 = mol Ba(OH)2reacted + mol Ba(OH)2 unreacted 0.012375 mol = 0.009375 mol + mol Ba(OH)2unreacted mol Ba(OH)2 unreacted = 0.003 mol mol of OH- = 2 x 0.003 mol = 0.006 mol Molarity of OH- = 0.006 mol OH-total volume (L) = 0.006 mol 300 x 10-3 L = 0.02 M OH-
  • 41. Example (2): A 50.00 mL sample of aqueous Ca(OH)2 requires 34.66 mL of 0.0980 M HNO3 for neutralization. What is the concentration of Ca(OH)2. Ca(OH)2(aq) + 2HNO3(aq) → Ca(NO3)2(aq) + 2H2O(ℓ) mol of HNO3 = 0.098 (mol/L) x 34.66x10-3 L = 3.4 x10-3 mol mol of Ca(OH)2 = 3.4 x 10-3 mol HNO3 x 2 mol HNO3 41 1 mol Ca(OH)2 = 1.7 x 10-3 mol Ca(OH)2 molarity of Ca(OH)2= 1.7 x 10-3 mol 50 x 10-3 L = 0.034 M
  • 42. 3) Oxidation-Reduction (called Redox) Reactions: For the following reaction: 2 Na(s) + Cl2(g) → 2 NaCl(s) Na is a neutral atom react with Cl2 which is also a neutral compound to form NaCl which contain Na+ and Cl- ions. Reactions like this one, which involves the transfer of electrons, are called oxidation-reduction (or redox) reactions. Many important redox reactions occur in our daily life, e.g.: Photosynthesis, combustion of sugar in our body,..etc. To explain how electrons are transfer, the concept of oxidation states must be introduced. 42
  • 43. 43 Oxidation States The concept of oxidation states (or oxidation numbers) provides a way of keeping track of the electrons in oxidation reduction reactions. need the rules for assigning oxidation states (memorize). The sum of the oxidation states must be zero in compounds or equal the charge of the ion. The following table summarized the rules for assigning the oxidation states
  • 44. 44 …The oxidation state of summary examples • elements in their standard states is zero Element: 0 Na(s), O2(g) , Hg(ℓ) •monoatomic ions are the same as their charge. Monoatomic ions: Charge of ion Na+ , Cl-, Ca+2 •Oxygen is assigned an oxidation state of -2 in its covalent compounds except as a peroxide (O2 -2, oxygen is -1, e.g. H2O2) Oxygen : -2 H2O , CO2 , CO •hydrogen is assigned the oxidation state +1, except when it bonded to metals; LiH, NaH …, its oxidation state is -1 Hydrogen: +1 HCN, HCl, NH3 •fluorine is always –1 in its compounds. Flourine: -1 HF, PF3
  • 45. The following figure shows oxidation numbers of familiar elements, arranged according to their position in the periodic table. 45
  • 46. Example: Assign the oxidation states to each element in the following compounds. CO2 : O is -2, so -2 x 2 + C = 0 C = +4 NO3 46 - : O is -2, so (3 x -2)+ N = -1 N = +5 H2SO4 : H is +1, O is -2, so [2x(+1)]+[(4x(-2)]+S =0 S = +6 FeO: O is -2, so [3x(-2)]+ 2xFe = 0 Fe = +3 23 CrO-2 : 2xCr +[7x(-2)]= -2 Cr = +6 27
  • 47. Oxidation-reduction reactions are characterized by the transfer electrons, so the oxidation states change. For the following reactions: 1) 2 Na + Cl2 → 2NaCl Oxidation state 0 0 +1 -1 47 2) CH4 + 2O2 → CO2 + 2H2O Oxidation state -4 +1 (each H) 0 +4 -2 (each O) +1 each H -2 Carbon undergoes a change in oxidation state from -4 in CH4 to +4 in CO2, 8 electrons (symbol e- stands for electrons) are lost
  • 48. 48 CH4 → CO2 + 8 e- -4 +4 Each oxygen change from an oxidation state 0 in O2 to -2 in H2O and CO2 , each atom gain 2 electrons. Since four oxygen atoms are involved , this is a gain of 8 electrons. O2 + 8 e- → CO2 + 2 H2O 0 4 x (-2)= - 8 No change occurs in the oxidation state of hydrogen .
  • 49. We can now define some important terms: Oxidation is the loss of electrons or an increase in oxidation state - lose electrons. . Reduction is the gain of electrons or a decrease in oxidation state - gain electrons. The substance that is oxidized is called the reducing agent. Reducing agent gets oxidized. Loses electrons. More positive oxidation state. The substance that is reduced is called the oxidizing agent. Oxidizing agent gets reduced. Gains electrons. More negative oxidation state. 49
  • 50. 50 Example: For the following reactions, identify Substance oxidized Substance reduced Oxidizing agent Reducing agent 1) Fe (s) + O2(g) → Fe2O3(s) 0 0 + 3 -2 The oxidation state for Fe increase from 0 to +3. thus Fe is oxidized. The oxidation state for O decrease from 0 to -2. thus O is reduced. The oxidizing agent is O2. The reducing agent is Fe.
  • 51. +3 -2 +2 -2 0 +4 -2 The oxidation state for C increase from +2 to +4. thus C is oxidized. The oxidation state for Fe decrease from +3 to 0. thus O is reduced. The oxidizing agent is Fe. The reducing agent is CO. 51 2) Fe2O3(s) + 3 CO(g) → 2 Fe(s) + 3 CO2(g) 3) SO3 2- + H+ + MnO4 - → SO4 2- + H2O + Mn2+ +4 -2 +1 +7 -2 +6 -2 +1 -2 +2 The oxidation state for S increase from +4 to +6. thus S is oxidized. The oxidation state for Mn decrease from +7 to +2. thus Mn is reduced. The oxidizing agent is MnO-. 4 The reducing agent is SO3 2-.
  • 52. 52 Balancing oxidation-reduction equations It is difficult to balance redox equations by simple inspection, the technique used for balancing redox reactions called the half-reaction method. All redox reactions can be thought of as happening in two halves. One produces electrons - Oxidation half. The other requires electrons - Reduction half. Write the half reactions for the following. 1) Na + Cl2 → Na+ + Cl- 2) Ce+4 + Sn+2 → Ce+3 + Sn+4
  • 53. 53 1) Na + Cl2 → Na+ + Cl- Na → Na+ oxidation Cl2 → Cl- reduction 2) Ce+4 + Sn+2 → Ce+3 + Sn+4 Ce+4 → Ce+3 reduction Sn+2 → Sn+4 oxidation The method for balancing redox equations differ slightly depending on whether the reaction takes place in acidic or basic solution.
  • 54. Balancing Redox Equations in acidic solution In aqueous solutions the key is the number of electrons produced must be the same as those required. For reactions in acidic solution an 8 step procedure. 1.Write separate equations for the oxidation-reduction half reactions 2. For each half reaction balance all reactants except H and O 3. Balance O using H2O 4. Balance H using H+ 5. Balance charge using e- 6. Multiply equations to make electrons equal 7. Add the half-reactions, and cancel identical species 8 Check that charges and elements are balanced. 54
  • 55. 55 Examples: Balance the following oxidation-reduction reactions occur in acidic aqueous solution. 1) MnO- + Fe+2 → Mn+2 + Fe+3 4 1) Write the half reactions MnO4 - → Mn+2 Fe+2 → Fe+3 2) Balance each half-reaction: MnO4 - → Mn+2 -Mn is balanced -balance oxygen by adding 4H2O to the write side of the equation. - Balance hydrogen by adding 8H+ to the left side of equation. 8H+ + MnO4 - → Mn+2 + 4H2O
  • 56. 56 -Balance the charge using electrons 8H+ + MnO4 - → Mn+2 + 4H2O +8 -1 → +2 0 +7 +2 equalize the charges by adding five electrons to the left side. 5e- + 8H+ + MnO4 - → Mn+2 + 4H2O reduction +2 +2 both the elements and charges are now balanced. For the oxidation reaction: Fe+2 → Fe+3 + e- +2 +3-1 +2 +2
  • 57. Equalize the electron transfer in the two half-reactions 57 5e- + 8H+ + MnO4 - → Mn+2 + 4H2O 5 Fe+2 → 5 Fe+3 + 5e- 8H+ + MnO4 - + 5 Fe+2 → Mn+2 + 4H2O + 5 Fe+3 check that elements and charges are balanced. elements balance: 5Fe, 1Mn, 4O, 8H→ 5Fe, 1Mn, 4O, 8H charge balance: 8(+1)+(-1)+5(+2)→(+2)+0+5(+3) +17 → +17 the equation is balanced.
  • 58. 58 2) Cu + NO3 - → Cu+2 + NO(g) 3 / Cu → Cu+2 + 2e- 2 / 3e- + 4H+ + NO3 - → NO + 2H2O 3Cu + 8H+ + 2NO3 - → 3Cu+2 + 2NO + 4H2O 3) Mn+2 + BiO3 - → Bi+3 + MnO4 - 2 / 4 H2O + Mn+2 → MnO4 - + 8H+ +5e- +2 +7 5/ 2e- + 6H+ +BiO3 - → Bi+3 + 3H2O +5 +3 2Mn+2 + 5BiO3 - + 14H+ → 2MnO4 - + 5Bi+3 + 7H2O
  • 59. Balancing Redox Equations in basic solution Do everything you would with acid, but add one more step. Add enough OH- to both sides to neutralize the H+ Makes water Examples: Balance the following equation in basic solutions: 59 Cr(OH)3 + OCl- + OH- → CrO4 2- + Cl- + H2O
  • 60. Cr(OH)3 + OCl- + OH- → CrO4 60 2- + Cl- + H2O 2/ Cr(OH)3 + H2O → CrO4 2- + 5H++3e- 0 +3 3/ 2e- + OCl- + 2H+ → Cl- + H2O +1 -1 2- + 3Cl- +H2O +4H+ (acidic solution) 2Cr(OH)3 + 3OCl- → 2CrO4 4OH- +2Cr(OH)3 + 3OCl- → 2CrO4 2- + 3Cl- +H2O + 4H+ + 4OH- 4OH- +2Cr(OH)3 + 3OCl- → 2CrO4 2- + 3Cl- +5H2O (basic solution)
  • 61. Example: 16.42 mL of 0.1327 M KMnO4 solution is needed to oxidize 25.00 mL of an acidic FeSO4 solution. What is the molarity of the iron solution: 5Fe2+ + MnO4 - + 8H+ Mn2+ + 5Fe3+ + 4H2O 0.01642 L 0.1327 mol KMnOx 4 1 L x 5 mol Fe2+ 1 mol KMnO4 x 1 0.02500 L Fe2+ = 0.4358 M Fe2+ 61 61