chapter4 e-learning

Chapter 4
(in solution)
Types of Chemical Reactions
and Solution Stoichiometry
水溶液中的化學與計量學
黃俊嬴
醫藥暨應用化學系; Lab: N1128
Tel: (07)312-1101*2810
Mail: genin@kmu.edu.twc
Section 4.1
Water, the Common Solvent
4.1 Water, the Common Solvent

4.2 The Nature of Aqueous Solutions: Strong and Weak
Electrolytes
4.3 The Composition of Solutions
4.4 Types of Chemical Reactions
4.5 Precipitation Reactions
4.6 Describing Reactions in Solution
4.7 Stoichiometry of Precipitation Reactions
4.8 Acid–Base Reactions
4.9 Oxidation–Reduction Reactions
4.10 Balancing Oxidation–Reduction Equations
Section 4.1
 One of the most important

substances on Earth.
 Can dissolve many different
substances.
 A polar molecule because of its
unequal charge distribution.
• We need to discuss the nature of

solutions in which water is the
dissolving medium, or solvent.
• These solutions are called aqueous
solutions (水溶液).
Section 4.1
學習目標
1. 了解最常見的溶劑—水的特性。
2. 了解電解質的一些特性
3. 學會描述一溶液之組成
Section 4.1
Formation of electrolyte aqueous

solution (Hydration; 水合)
Interaction between water and ethanol
*Polar water molecules interact with
the positive and negative ions of a salt,
(nonelectrolyte; miscible 互溶)
assisting in the dissolving process.
*Solubility depends on the interaction between solutes and solvent

5
Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Nature of Aqueous Solutions
 Solute – substance being dissolved.
 Solvent – liquid water.
 Electrolyte – substance that when dissolved in water
produces a solution that can conduct electricity.
 Strong Electrolytes – conduct current very efficiently (bulb shines
brightly). Completely ionized in water.
 Weak Electrolytes – conduct only a small current (bulb glows dimly). A
small degree of ionization in water.
 Nonelectrolytes – no current flows (bulb remains unlit). Dissolves but
does not produce any ions.
As Arrhenius postulated, the extent to which a solution can conduct

an electric current depends directly on the number of ions present.
Section 4.2
強電解質弱電解質非電解質

https://www.youtube.com/watch?v=mYjfdBFAtzc https://www.youtube.com/watch?v=a8LbduvNIso
7
Section 4.2
When solid NaCl dissolves, the Na＋ and Cl－

ions are randomly dispersed in the water.
8
Section 4.2
HCl(aq) is completely ionized.
NaOH(aq) HCl (aq)

9
Section 4.2
Acetic acid (HC2H3O2) exists in

water mostly as undissociated
molecules. Only a small
percentage of the molecules are
ionized.
NH3 + H2O  NH4+ + OH-
NH3(aq) CH3COOH(aq)
10
Section 4.2
Svante August Arrhenius
電解質理論、酸鹼理論
阿瑞尼斯方程式
生理學
地質學 (冰河時期的起源)
天文學
https://www.youtube.com/watch?v=0HXTGoOnMrU
11
Section 4.3
The Composition of Solutions
Chemical Reactions of Solutions

 We must know:
 The nature of the reaction.
 The amounts of chemicals present in the solutions. 
溶液的組成
[ ]
Section 4.3
Molarity KK: [moˈlærɪti] 體積莫爾濃度

 Molarity (M) = moles of solute per volume of
solution in liters:
moles of solute
M = Molarity =
liters of solution
6 moles of HCl
3 M HCl =
2 liters of solution
Molality 重量莫爾濃度 moles/kg

Section 4.3
Concentration of Ions (Assuming 100% ionization)

 For a 0.25 M CaCl2 solution:
CaCl2 → Ca2+ + 2Cl–
 Ca2+: 1 × 0.25 M = 0.25 M Ca2+

 Cl–: 2 × 0.25 M = 0.50 M Cl–.
Section 4.3
Dilution 稀釋
 The process of adding water to a concentrated or stock
solution to achieve the molarity desired for a particular
solution.
 Dilution with water does not alter the numbers of moles
of solute present.
 Moles of solute before dilution = moles of solute after
dilution
M1V1 = M2V2
15
Section 4.3
重點整理
Section 4.4
Types of Chemical Reactions (in aqueous solutions)
 Precipitation Reactions
 Acid–Base Reactions
 Oxidation–Reduction Reactions
Section 4.4
Types of Chemical Reactions
學習目標
1.了解沉澱反應的行為並記憶沉澱的規則。
2. 學習以不同的方式描述一化學反應式。
3. 熟練沉澱反應之化學記量學。
4. 了解甚麼叫做酸鹼反應以及熟練酸鹼反應之化學計量學
5. 了解甚麼叫做氧化還原反應(到底發生甚麼事)
6. 學會平衡一氧化還原反應之反應式
Section 4.5
Precipitation Reactions
Precipitation Reaction
 A double displacement reaction in which a solid forms

and separates from the solution.
 When ionic compounds dissolve in water, the

resulting solution contains the separated ions.
 Precipitate – the solid that forms.

Section 4.5
The Reaction of K2CrO4(aq) and Ba(NO3)2(aq)

 Ba2+(aq) + CrO42–(aq) → BaCrO4(s)
Section 4.5
Precipitates
 Soluble – solid dissolves in solution; (aq) is used in
reaction equation.
 Insoluble – solid does not dissolve in solution; (s) is used

in reaction equation.
 Insoluble and slightly soluble are often used

interchangeably.
Section 4.5
Simple Rules for Solubility (記起來)

1. Most nitrate (NO3-) salts are soluble.
2. Most alkali metal (group 1A) salts and NH4+ are soluble.
3. Most Cl-, Br-, and I- salts are soluble (except Ag+, Pb2+,
Hg22+).
4. Most sulfate salts are soluble (except BaSO4, PbSO4,
Hg2SO4, CaSO4).
5. Most OH- are only slightly soluble (NaOH, KOH are
soluble, Ba(OH)2, Ca(OH)2 are marginally soluble).
6. Most S2-, CO32-, CrO42-, PO43- salts are only slightly soluble,
except for those containing the cations in Rule 2.
Section 4.5
Sample Exercise 4.8 Predicting Reaction Products

Predict what will happen when the following pairs of
solutions are mixed.
a. KNO3(aq) and BaCl2(aq)

b. Na2SO4(aq) and Pb(NO3)2(aq)
c. KOH(aq) and Fe(NO3)3(aq)
23
Section 4.6
Describing Reactions in Solution
Formula Equation (Molecular Equation)

你丟了甚麼進去溶液裡面
Complete Ionic Equation
實際上在溶液裡面變成甚麼
Net Ionic Equation

真正參與反應的物種
Section 4.6
Formula Equation (Molecular Equation)

 Gives the overall reaction stoichiometry but not
necessarily the actual forms of the reactants and products
in solution.
 Reactants and products generally shown as compounds.
 Use solubility rules to determine which compounds are
aqueous and which compounds are solids.
AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)

Section 4.6
Complete Ionic Equation
 All substances that are strong electrolytes are represented as ions.
Ag+(aq)+ NO3-(aq)+ Na+(aq) + Cl-(aq)  AgCl(s) + Na+(aq)+ NO3-(aq)
Net Ionic Equation

 Includes only those solution components undergoing a change.
 Show only components that actually react.
Ag+(aq) + Cl-(aq) AgCl(s)
觀眾
 Spectator ions are not included (ions that do not participate
directly in the reaction).
 Na+ and NO3- are spectator ions.
Section 4.7
Stoichiometry of Precipitation Reactions
Solving Stoichiometry Problems for Reactions in Solution
1. Identify the species present in the combined solution,

and determine what reaction occurs.
2. Write the balanced net ionic equation for the reaction.
3. Calculate the moles of reactants.
4. Determine which reactant is limiting (limiting reagent).
5. Calculate the moles of product(s), as required.
6. Unit conversions, as required.
Section 4.7
CONCEPT CHECK I
10.0 mL of a 0.30 M sodium phosphate solution reacts
with 20.0 mL of a 0.20 M lead(II) nitrate solution
(assume no volume change).
 What precipitate will form?
lead(II) phosphate, Pb3(PO4)2
 What mass of precipitate will form?
1.1 g Pb3(PO4)2
Section 4.7
The balanced molecular equation is:
2Na3PO4(aq) + 3Pb(NO3)2(aq) → 6NaNO3(aq) + 1Pb3(PO4)2(s).
0.0030 mol Na3PO4 present to start and 0.0040 mol Pb(NO3)2

present to start.
Pb(NO3)2 is the limiting reactant, therefore 0.0013 mol of

Pb3(PO4)2 is produced.
Since the molar mass of Pb3(PO4)2 is 811.54 g/mol,
1.1 g of Pb3(PO4)2 will form.
29
Section 4.7
CONCEPT CHECK II
 What is the concentration of nitrate ions left in

solution after the reaction is complete?
0.2*2*20/30 0.27 M
Section 4.7
CONCEPT CHECK III

 What is the concentration of phosphate ions left

in solution after the reaction is complete?
0.011 M
{10*0.3-[(2*0.2*20)/3]}/30 ; Pb3(PO4)2
Section 4.8
Acid‐Base Reactions
Acid–Base Reactions (Brønsted–Lowry)

 Acid—proton donor
 Base—proton acceptor
 For a strong acid and base reaction:
H+(aq) + OH–(aq) H2O(l)
Section 4.8
 When an aqueous solution of HCl is mixed with an aqueous

solution of NaOH, the combined solution contains the ions H
＋, Cl－, Na＋, and OH－.
 We can see that NaCl is soluble in water and thus will not
precipitate.
 Large quantities of H＋ and OH－ ions cannot coexist in
solution.
They react to form H2O molecules:

H＋(aq) ＋ OH－(aq) → H2O(l)
33
Section 4.8
 Consider mixing an aqueous solution of acetic acid with an

aqueous solution of KOH.
 A possible precipitation reaction could occur between K＋
and OH－.
 We know that KOH is soluble, so precipitation does not
occur.
The net ionic equation for this reaction is
OH－＋ HC2H3O2 (aq) → H2O(l) ＋ C2H3O2－(aq)
34
Section 4.8
This reaction illustrates a very important general

principle:
The OH- is such a strong base that for purposes of

stoichiometric calculations it can be assumed to react
completely with any weak acid that we will
encounter.
*強加弱 完全反應
35
Section 4.8
Performing Calculations for Acid–Base Reactions

1. List the species present in the combined solution before
any reaction occurs, and decide what reaction will
occur.
2. Write the balanced net ionic equation for this reaction.
3. Calculate moles of reactants.
4. Determine the limiting reactant, where appropriate.
5. Calculate the moles of the required reactant or product.
6. Unit conversion, as required.
Section 4.8
Acid–Base Titrations
 Titration – delivery of a measured volume of a solution of known
concentration (the titrant) into a solution containing the substance
being analyzed (the analyte).
 Equivalence point – enough titrant added to react exactly with the

analyte. (等量點)
 Endpoint – the indicator changes color so you can tell the

equivalence point has been reached. (終點)
Section 4.8
The following three requirements must be met

for a titration to be successful:
1. The exact reaction between titrant and analyte
must be know.
2. The stoichiometric (equivalence) point must be
marked accurately.
3. The volume of titrant required to reach the
stoichiometric point must be known accurately.
38
Section 4.8
 When an acid is titrated with a (a) (b)
base, the phenolphthalein (酚酞)

remains colorless until after the
acid is consumed and the first
drop of excess base is added.
 In this case, the endpoint (the

solution changes from colorless
The titration of acid with a base. (a) The titrant
to pink) occurs approximately (the base) is in the buret, and the flask
contains the acid solution along with a small
one drop of base beyond the amount of indicator. (b) As base is added
drop by drop to the acid solution in the flask
stoichiometric point. during the titration, the indicator changes
color, but the color disappears on mixing.
39
Section 4.8
(c)
(c) The stoichiometric

(equivalence) point is marked by a
permanent indicator color change.
The volume of base added is the
difference between the final and
initial buret readings.
*multiequilibria in the solution
40
Section 4.8
A student carries out an experiment to standardize a NaOH solution.

To do this, the student weighs out a 1.3009 g sample of potassium
hydrogen phthalate (鄰苯二甲酸氫鉀, KHC8H4O4, often abbreviated
KHP). KHP (molar mass 204.22 g/mol) has one acidic hydrogen.
The student dissolves the KHP in distilled water, adds phenolphthalein

as an indicator, and titrates the resulting solution with the NaOH
solution to the phenolphthalein endpoint. The different between the
final and initial buret readings indicates that 41.20 mL of the NaOH
solution is required to react exactly with the 1.3009 g KHP
Calculate the concentration of the NaOH solution.
41
Section 4.8
* KHP is a primary standard (一級標準品)

(1) 純度高; (2) 在空氣中穩定
(3) 不含結晶水，不易潮解;
(4) 容易取得; (5) 良好的溶解度;
(6) 分子量大
鄰苯二甲酸氫鉀
常用來與配好的標準溶液滴定， (KHP)
確認標準溶液的濃度
Other primary standard: Na2CO3, NaCl,…
42
Section 4.8
Solution
Aqueous NaOH contains the Na＋ and OH－ ions, and
KHC8H4O4 dissolves in water to give the K＋
and HC8H4O4－ ions. As the titration proceeds, the mixed
solution contains the following ions: K＋, HC8H4O4－,
Na＋, OH－. The OH－ will remove an H＋ from the
HC8H4O4－ to give the following net ionic reaction:
43
Section 4.8
Since the reaction exhibits 1:1 stoichiometry, we know
that 41.20 mL of the NaOH solution must contain exactly
the same number of moles of OH－ as there are moles of
HC8H4O4－ in 1.3009 g KHC8H4O4. We calculate the
moles of KHC8H4O4 in the usual way:
This means that 6.3701 × 10－3 mol OH－ must be added

to react with the 6.3701 × 10－3 mol HC8H4O4－. Thus
44
Section 4.8
41.20 mL (4.120 × 10－2 L) of the NaOH solution must

contain 6.3701 × 10－3 mol OH－ (and Na＋), and the
concertration of the sodium hydroxide solution is
This standard sodium hydroxide solution can now be

used in other experiments.
45
Section 4.9
Oxidation‐Reduction Reactions
Redox Reactions
 Reactions in which one or more electrons are
transferred.
Reaction of Sodium
and Chlorine
46
Section 4.9
 We do this as follows: For a covalent bond

between two identical atoms, the electrons are
split equally between two atoms.
 In cases where two different atoms are involved

(and the electrons are thus shared unequally), the
shared electrons are assigned completely to the
atom that has the stronger attraction for electrons.
47
Section 4.9
Rules for Assigning Oxidation States
(氧化數;與元素態時的原子相比)
48
Section 4.9
Rules for Assigning Oxidation States
1. Sum of oxidation states = 0 in compounds
2. Sum of oxidation states = charge of the

ion in ions
Section 4.9
EXERCISE
Find the oxidation states for each of the elements in

each of the following compounds:
 K2Cr2O7 K = +1; Cr = +6; O = –2

 CO32- C = +4; O = –2
 MnO2 Mn = +4; O = –2
 PCl5 P = +5; Cl = –1
 SF4 S = +4; F = –1
Section 4.9
Redox Characteristics
 Transfer of electrons.
 Transfer may occur to form ions.
 Oxidation – increase in oxidation state (loss of electrons);
reducing agent.
 Reduction – decrease in oxidation state (gain of
electrons); oxidizing agent.
Section 4.9
CONCEPT CHECK!
Which of the following are oxidation-reduction

reactions? Identify the oxidizing agent and the
reducing agent.
a)Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)

b)Cr2O72-(aq) + 2OH-(aq) 2CrO42-(aq) + H2O(l)
c)2CuCl(aq) CuCl2(aq) + Cu(s)
Section 4.10
Balancing Oxidation‐Reduction Equations
Balancing Oxidation–Reduction Reactions by
Oxidation States
1. Write the unbalanced equation.
2. Determine the oxidation states of all atoms in the
reactants and products.
3. Show electrons gained and lost using “tie lines.”
4. Use coefficients to equalize the electrons gained and lost.
5. Balance the rest of the equation by inspection.
6. Add appropriate states.
Section 4.10
 Balance the reaction between solid zinc and

aqueous hydrochloric acid to produce aqueous
zinc(II) chloride and hydrogen gas.
1. What is the unbalanced equation?
 Zn(s) + HCl(aq)  Zn2+(aq) + Cl–(aq) + H2(g)
2. What are the oxidation states for each atom?

 Zn(s) + HCl(aq)  Zn2+(aq) + Cl–(aq) + H2(g)
0 +1 –1 +2 –1 0
Section 4.10
3. How are electrons gained and lost?

1 e– gained (each atom)
 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

0 +1 –1 +2 –1 0
2 e– lost
 The oxidation state of chlorine remains unchanged.

Section 4.10
4. What coefficients are needed to equalize the electrons
gained and lost?
1 e– gained (each atom) × 2
 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

0 +1 –1 +2 –1 0
2 e– lost
 Zn(s) + 2HCl(aq)  Zn2+(aq) + Cl–(aq) + H2(g)
5. What coefficients are needed to balance the remaining

elements?
 Zn(s) + 2HCl(aq)  Zn2+(aq) + 2Cl–(aq) + H2(g)
Section 4.10
57
Section 4.10
The Half–Reaction Method for Balancing Equations

for Oxidation–Reduction Reactions Occurring in
Acidic Solution
1. Write separate equations for the oxidation and

reduction half–reactions.
reactions
2. For each half–reaction:
– Balance all the elements except H and O.
O
– Balance O using H2O.
– Balance H using H+.
– Balance the charge using electrons (e-).
58
Section 4.10
The Half–Reaction Method for Balancing Equations

for Oxidation–Reduction Reactions Occurring in
Acidic Solution
3. If necessary, multiply one or both balanced half–

reactions by an integer to equalize the number of
electrons transferred in the two half–reactions.
4. Add the half–reactions, and cancel identical species.
5. Check that the elements and charges are balanced.
59
Section 4.10
These steps are summarized by the following flowchart:
*Acidic solution
60
Section 4.10
61
Section 4.10
62
Section 4.10
63
Section 4.10
Half-Reaction Method - Balancing in Base
Section 4.10
Section 4.10
重點整理

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Chapter 4

4.1 Water, the Common Solvent

 One of the most important

• We need to discuss the nature of

Formation of electrolyte aqueous

*Solubility depends on the interaction between solutes and solvent

As Arrhenius postulated, the extent to which a solution can conduct

強電解質 弱電解質 非電解質

When solid NaCl dissolves, the Na＋ and Cl－

HCl(aq) is completely ionized.

NaOH(aq) HCl (aq)

Acetic acid (HC2H3O2) exists in

Chemical Reactions of Solutions

Molarity KK: [moˈlærɪti] 體積莫爾濃度

Molality 重量莫爾濃度 moles/kg

Concentration of Ions (Assuming 100% ionization)

 Ca2+: 1 × 0.25 M = 0.25 M Ca2+

 A double displacement reaction in which a solid forms

 When ionic compounds dissolve in water, the

 Precipitate – the solid that forms.

The Reaction of K2CrO4(aq) and Ba(NO3)2(aq)

 Insoluble – solid does not dissolve in solution; (s) is used

 Insoluble and slightly soluble are often used

Simple Rules for Solubility (記起來)

Sample Exercise 4.8 Predicting Reaction Products

a. KNO3(aq) and BaCl2(aq)

Formula Equation (Molecular Equation)

Net Ionic Equation

Formula Equation (Molecular Equation)

AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)

Net Ionic Equation

Solving Stoichiometry Problems for Reactions in Solution

1. Identify the species present in the combined solution,

The balanced molecular equation is:

2Na3PO4(aq) + 3Pb(NO3)2(aq) → 6NaNO3(aq) + 1Pb3(PO4)2(s).

0.0030 mol Na3PO4 present to start and 0.0040 mol Pb(NO3)2

Pb(NO3)2 is the limiting reactant, therefore 0.0013 mol of

Since the molar mass of Pb3(PO4)2 is 811.54 g/mol,

1.1 g of Pb3(PO4)2 will form.

 What is the concentration of nitrate ions left in

CONCEPT CHECK III

 What is the concentration of phosphate ions left

Acid–Base Reactions (Brønsted–Lowry)

 When an aqueous solution of HCl is mixed with an aqueous

They react to form H2O molecules:

 Consider mixing an aqueous solution of acetic acid with an

The net ionic equation for this reaction is

OH－ ＋ HC2H3O2 (aq) → H2O(l) ＋ C2H3O2－(aq)

This reaction illustrates a very important general

The OH- is such a strong base that for purposes of

Performing Calculations for Acid–Base Reactions

 Equivalence point – enough titrant added to react exactly with the

 Endpoint – the indicator changes color so you can tell the

The following three requirements must be met

 When an acid is titrated with a (a) (b)

base, the phenolphthalein (酚酞)

 In this case, the endpoint (the

(c) The stoichiometric

*multiequilibria in the solution

A student carries out an experiment to standardize a NaOH solution.

The student dissolves the KHP in distilled water, adds phenolphthalein

Calculate the concentration of the NaOH solution.

* KHP is a primary standard (一級標準品)

Other primary standard: Na2CO3, NaCl,…

強電解質弱電解質非電解質

OH－＋ HC2H3O2 (aq) → H2O(l) ＋ C2H3O2－(aq)