Solution Stoichiometry & Chemical Analysis

Chapter 4

Solution – a homogenous mixture

Solvent – the dissolving medium (it does the dissolving)
Solute – the substance that gets dissolved (is dispersed throughout the solvent)

Water as a Solvent
 H2O has covalent bonds (2 nonmetals)
 O attracts the shared electrons more and becomes negatively charged
 H has the shared electrons less of the time and becomes positively charged
 Because it is bent H2O is a polar molecule

H    +       –  

~105   
O

H 
 If H2O is the solvent the solution is an “aqueous” solution
 Many Ionic compounds are soluble in H2O
 Ions are attracted to oppositely charged parts of a H2O molecule
 H2O molecules surround the ion and move it away from the rest of the solute (hydration)

 If an ionic compound is soluble in H2O, it is 100% dissociated into cations and anions  

 ex: H 
Al(H2O)6+3 hydration number
H    - the number of
  O     H  H2O molecules
needed to dissolve
O     H  O    H  that ion (in
many cases 2x
 
Al+3  charge)
H 
(p135 – good
O    H  pictures)
O       H 
 
  O    H 
H 
H   

H 
  H2O can also dissolve polar substances that are not ionic
 ex: Ethanol
           H    H 

            |      |                                         H 

    H – C – C – O                         O 

            |      |                                         

Hydrogen Bonding

In general, Like dissolves Like:

- polar solvents dissolve polar solutes (or ionic solutes)
- nonpolar solvents dissolve nonpolar solutes

Some solutes produce solutions that conduct electricity

- Electrolyte
o Any substance whose H2O solution conducts electricity
o It conducts because the solution contains ions that move freely (Svante Arrhenius)
o Strong Electrolyte – dissociates 100%; are good conductors
 Soluble salts, strong acids, strong bases
 Ex. NaCl(s)  Na+(aq) + Cl-(aq) is 100%
 Strong Acids: HClO4, NHO3, H2SO4, HBr, HI, HCl
 Strong Bases: all alkali metal hydroxides, Ba(OH)2, Ca(OH)2
o Weak Electrolytes
 Only form a few ions; poor conductors
 Weak acids and weak bases
 Ex. HC2H3O2  H+(aq) + C2H3O2-(aq)
NH3(g) + H2O  NH4+(aq) + OH-(aq)
Most common weak base – NH3

Many reactions are performed in solution

- To perform stoichiometric calculations you must know
o What type of reaction is occurring (precipitation, acid-base, redox)
o The amount of solutes dissolved in the solutions

Molarity (M)
 - The number of moles of solute dissolved per liter of solution
mol solute
M
o L solution

Ex. 4.1 (p141) 11.5g NaOH in 1.50L of solution Molarity=?

- The concentration is given in terms of the form of solute before it dissociates

- 0.192M NaOH actually contains 0.192M Na+ and 0.192M OH- (100% dissociation)
Ex. 4.3 (p143) a) Co(NO3)2 (s) H2O
b) FeCl3 (s) H2O

- The number of moles of solute particles present can be calculated from known molarity
and volume
o mol=MxV

Ex. 4.4 (p143) Calculate the number of moles of Cl- ions in 1.75L of 1.0x10-3M ZnCl2

Ex. 4.5 (p144) Typical blood serum is about 0.14M NaCl.

What volume of blood contains 1.0mg of NaCl?

When you perform a reaction, you use a solution that you have made up and know the
concentration of.
It’s called a …
Standard Solution
- a solution whose concentration is accurately known
- for solid solutes
o weigh out the solute and put it in a volumetric flask
o add some H2O to dissolve the solute
o add H2O until the solution has the desired volume

Ex. 4.6 (p144) How do you prepare 1.00L of a 0.200M K2Cr2O7 solution?
Stock Solution
- a very concentrated solution purchased from a chemical company
- to prepare a standard solution from a stock solution:
1. calculate the number of moles of solute needed in the standard solution
(mol=MxL)
2. calculate what volume of stock solution contains that number of moles of solute
(V=mol/M)
3. put that amount of stock solution in a volumetric flask and add H2O until you
reach the correct volume

Ex. 4.7 (p146) What volume of 16M H2SO4 must be used to prepare 1.5L of 0.10M
H2SO4 solution?

Stoichiometry Problems Using Solution Reactions

- from the information in the question you must be able to write a balanced equation
- it will be one of these types of reactions:
1. precipitation reactions
2. acid/base reactions
3. oxidation-reduction reactions

 Write down the formulas for the reactants & determine what type of reaction is occurring!  

- reactions can be described by different types of equations:

1. Molecular Equation
 Gives overall reaction but not the actual forms of the reactants and products
 Ex. NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l)
2. Ionic Equation
 Shows reactants and products that are strong electrolytes as separate ions
 Ex. Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq)  Na+(aq) + Cl-(aq) + H2O(l)
3. Net Ionic Equation
 Shows only the components of the solution that undergo change
 Does not include “Spectator Ions” (do not change in any way)
 Ex. OH-(aq) + H+(aq)  H2O(l)
Precipitation Reactions
- A reaction that forms an insoluble product
- The insoluble product “precipitates” out of the solution
- Only ionic compounds containing certain cations & anions are soluble in H2O
 Cations
- All alkali metals (Li+, Na+, K+, Rb+, & Cs+) and NH4+ salts and bases are soluble
- Ba(OH)2 and Ca(OH)2 are also fairly soluble bases
Anions
- All nitrates (NO3-), chlorates (ClO3-), perchlorates (ClO4-), & acetates (C2H3O2-) are
soluble
- All halides (Cl-, Br-, & I-) are soluble ***Except with Ag+, Hg2+2, & Pb+2 are
insoluble
- All sulfates (SO4-2) are soluble ***Except with Ba+, Ca+2, & Pb+2 are insoluble

 All other types of common inorganic compounds are Insoluble!  

Ex. 4.8 (p152) a) KNO3 + BaCl2 

b) Na2SO4 + Pb(NO3)2 

c) KOH + Fe(NO3)3 

Selective Precipitation can be used in:

Qualitative Analysis (Chapter 15)
- An unknown substance is reacted with known solution
- It can be identified by what reactions occur & what precipitates are formed

Can also be used in:

Quantitative Analysis
- Used to determine how much of a compound or ion is present
1. Determine what reaction occurs
2. Write a balanced equation
3. Convert given amount to moles (find limiter)
4. Mole ratio  mol of new substance
5. Convert mol of new stuff to desired units

Ex. 4.11 (p156) 1.25L of 0.0500M Pb(NO3)2

2.00L of 0.0250M Na2SO4 }
 mixed 
How many grams of what precipitates?

Ex. Calculate the volume of 0.0100M NaOH required to precipitate all of the Fe+3 ions
contained in
1.75L of 0.0350M Fe(NO3)3.
 Ex. 500.0mL of 0.500M Na2SO4
350.mL of 0.750M CaCl2 }
 mixed 
How many grams of what precipitates?

Acid-Base Reactions
Arrhenius
Acid-produces H+(aq) when dissolved in H2O
HX  H+(aq) + X-(aq)
Bases-produces OH-(aq) when dissolved in H2O
MOH  M+(aq) + OH-(aq)

Bronsted-Lowry
Acid-proton donor (loses H+)
Base-proton acceptor (gains H+)

- Strong acids and bases in aqueous solution are 100% dissociated (written as ions)
- Weak acids in aqueous solution are written undissociated
- H+ and OH- always associate to form H2O
- OH-, a strong base, will react completely with a weak acid to produce H2O and the anion
of the acid
Ex. HC2H3O2 (aq) + OH-(aq)  H2O(l) + C2H3O2-(aq)
______________________________________________________________________________
____________
Ex. 4.12 (p159) What volume of a 0.100M HCl solution is needed to neutralize 25.0mL of
0.350M NaOH
solution?

Ex. 4.13 (p160) 28.0mL of 0.250M HNO3

}
53.0mL of 0.320M KOH  mixed 
a) Calculate the mass of H2O formed by this reaction
 b) What is the concentration of H+ or OH- in excess after the reaction goes
to completion?

Acid/base neutralization can be used in:

Titration
- A type of volumetric analysis
- React an acid (or base) of known concentration with a base (or acid) of unknown
concentration
- When the solution is neutralized mol H+ = mol OH-
- This is called the “equivalence point” or the “endpoint”
- At this point an indicator changes color

Ex. A chemist synthesized a new acid, which is known to have one acidic hydrogen per
molecule. A
2.321g sample of the pure acid was dissolved in H2O and titrated with 0.1031M
NaOH. It required
68.43mL to reach the stoichiometric point. Calculate the molar mass of the acid.

Oxidation-Reduction Reactions
- reactions where one or more electrons are transferred
Oxidation
- loss of electrons
- oxidation number increases
- the substance containing the particle being oxidized is the Reducing Agent
Reduction
- gain of electrons
- oxidation number decreases
- the substance containing the particle being reduced is the Oxidizing Agent

Leo Ger or Oil Rig 

Oxidation Number Rules

1. Free Element = 0
 2. In compounds
Group 1 = +1 (not H)
Group 2 = +2
3. In compounds, F = -1
4. In compounds, O = 2
except in peroxides O2-2
ex. H2O2, Na2O2
5. The total charge on a particle is the sum of all charges on the atoms in the particle
i. for compounds = 0
ii. for polyatomic ions = the ions charge

Ex. 4.16 (p167) Assign oxidation states to all the atoms in the following:
a) CO2 b) SF6 c) NO3-

Balancing Redox Reactions

- balance the electron transfer  = lose e‐ 
- finish balancing by inspection
 = gain e‐
Ex. MnO2 + Al  Mn + Al2O3

Ex. PH3 + O2  P4O10 + H2O

Ex. C2H5OH + Cr2O7-2 + H+  Cr+3 + CO2 + H2O

Redox Reactions in Acidic or Basic Solution

- many redox reactions occur in an acid or a base
- the H+ from the acid or OH- from the base take part in the reaction
- when balancing these equations, always start by balancing the electron transfer

In Acid Solution
 1. Balance the electron transfer
2. Add H2O to the side deficient in O
3. Add H+ to the side deficient in H
4. Check to be sure the charge is balanced

Ex. In acidic solution, H2SO3 is oxidized by Cr2O7-2 to form HSO4- and Cr+3
H2SO3 + Cr2O7-2  HSO4- + Cr+3

Ex. In acid solution:

NO3- + H2S  HSO4- + NH4+

In Basic Solution:
1. Balance electron transfer
2. Add H2O to the side deficient in O
3. Add H+ to the side deficient in H
4. Check to be sure charge is balanced
5. Add OH- to the H+’s to form H2O and add the same number of OH-’s to the other
side of the equation
6. Eliminate duplication of H2O

Ex. Zn + MnO2  Zn(OH)4-2 + MnO(OH)

Ex. 4.20 (p177) Ag + CN- + O2  Ag(CN)2-

 Ex. Chang 12.6 (p512) A 17.00mL volume of 0.1000M KMnO4 is needed to
oxidize 25.00mL of
a FeSO4 solution in acidic medium. What is the
concentration of the
FeSO4 solution?
given: Fe+2 + MnO4-  Mn+2 + Fe+3

Redox Titrations
- volumetric analysis using a redox reaction
- you measure the amount of solution that reacts with a standard solution

Ex. 4.30 (p143) 1.00L of an unknown Sn+2 solution required 46.45mL of a 0.1050M Ce+4
solution to
reach the stoichiometric point. Calculate the [Sn+2] in the unknown
solution.
Ce+4 + Sn+2  Ce+3 + Sn+4