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CHEMISTRY

Conspectus of lectures 2013

CONTENTS

Page 2 6 6 7 8 9 11 11 12 12 13 13 14 15 18 20 20 22 23

Thermochemistry and thermodynamics Aqueous solutions Solutions of acids and bases Water as an acid and a base The pH scale Acid-base properties of salts Oxidation - reduction reactions Rules for assignation of oxidation states Oxidizing and reducing agents Balancing redox equations Metal chemical properties Metal reactions with water Metal reactions with aqueous solutions of strong bases. Metal reactions with the acid aqueous solutions. Metal reactions with the aqueous solutions of salts. Electrochemistry Galvanic cells and cells potential The Nernst equation Metal corrosion and corrosion prevention

2 THERMOCHEMISTRY AND THERMODYNAMICS The nature of energy Although the concept of energy is quite well known, energy itself is rather difficult to define concisely. We will define energy as the capacity to do work or to cause heat transfer. In this chapter we will concentrate on the heat transfer that accompanies chemical processes. One of the most important characteristics of energy is that it is conserved. The law of conservation states that energy can be converted from one form to another but can be neither created nor destroyed. Energy can be classified as either potential energy or kinetic energy. Heat involves the transfer of energy between two objects due to a temperature difference. Work is defined as force acting over a distance. Thus, there are two ways to transfer energy: through work and through heat. The way that this energy transfer is divided between work and through heat depends on the specific conditions - the pathway. Energy change is independent from the pathway; however, work and heat are both dependent on the pathway. A property that is independent from the pathway is called a state function. Energy is a state function but work and heat are not state functions. Chemical energy Example - the combustion of methane: CH4 (g) + 2O2(g) CO2(g) + 2H2O(g) + Q (energy or heat) When a reaction results in the release of heat, it is said to be exothermic (exo - means out of) and energy flows out of the system. Example - the reaction of nitrogen with oxygen: N2(g) + O2(g) + Q (energy or heat) 2NO(g) Reactions that absorb energy from surroundings are said to be endothermic, that is heat flows into the system. To discuss these reactions we divide the universe into two parts: the system and the surroundings (Fig. 1). SURROUNDINGS SURROUNDINGS

ENERGY SYSTEM

ENERGY SYSTEM

3 E < 0 Fig. 1. Exothermic reaction E > 0 Endothermic reaction

The system is the part of the universe on which we wish to focus attention - in this case we define the system as the reactants and products. The surroundings include everything else in the universe - in this case surroundings consist of the reaction container, the room and anything else other than the reactants and products. The energy gained by the surroundings is equal to the energy lost by the system. The law of conversation of energy is often called the first law of thermodynamics and stated as follows: The energy of universe is constant. Enthalpy The heat of reaction is the quantity of heat released or absorbed during a chemical reaction. Chemical reactions are usually carried out in open vessels. Volumes may change in such vessels, but the pressure remains constant. The heat content at constant pressure is called enthalpy. The symbol for enthalpy is H. The change in heat content that occurs during any process is represented by H. If a process is exothermic, the total heat content of the products is lower than that of the reactants and H in this change is negative. The products of an endothermic reaction must have a higher heat content than the reactants and H in this change is positive. Enthalpy usually is given in kilo joules. When one mole of a compound is formed from its elements, the heat of reaction H, is called the heat of formation Hf. So the heat of formation of sodium sulphate Na2SO4: 2Na(s) + S(rhomb.) + 2O2(g) = Na2SO4(s) H = 1384,6 kJ The standard heat of formation, represented by the symbol Hf, is the heat resulting from the formation of 1 mole of a compound from elements at 298,15 K (25oC) and pressure 103,3 kPa (1 atmosphere). The chemical reaction is called a thermo chemical reaction if it contains indicated phases of substances and reaction heat. For example: H2(g) + 1/2O2(g) = H2O(l) + 285,84 kJ Oxygens coefficient is 1/2 because of equation balancing - to make the amount of water formed equal to 1 mole. Standard enthalpies of formation The standard enthalpy of formation Hfo of a compound is defined as the change in enthalpy, that accompanies the formation of 1 mole of a compound from its elements with all substances in their standard states at 298 K (25oC). The conventional definitions of standard states:

4 *0 For a gas the standard state is a pressure of exactly 1 atmosphere - 101,3 kPa; *1 For a substance present in a solution, the standard state is a concentration of exactly 1 M; *2 For a pure substance (liquid or solid), the standard state is the pure liquid or solid state; *3 For an element the standard state is a form in which the element exists under conditions of 1 atmosphere - 101,3 kPa and 298 K (25oC).

5 Hesss law Since enthalpy is a state function, the change in enthalpy when going from some initial state to some final state is independent of the pathway. This means that: In going from a particular set of reactants to a particular set of products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. Reaction can be carried out in one step: N2 (g) + 2O2 (g) = 2NO2 (g) Hf = 68 kJ This reaction can be carried out into two distinct steps: N2 (g) + O2 (g) = 2NO (g) H2 = 180 kJ 2NO (g) + O2 (g) = 2NO2 (g) H3 = 112 kJ N2 (g) + 2O2 (g) = 2NO2 (g) H1 = H2 +H3 = 68 kJ

The enthalpy change for a given reaction can be calculated by subtracting the enthalpies of formation of the reactants from the enthalpies of formation of the products: Horeaction = niHof products njHof reactants, ni and nj - the number of moles in reactions equation. While doing enthalpy calculations these key concepts must be observed: *4 When a reaction is reversed, the magnitude of H remains the same but its sign changes; *5 When the balanced equation of a reaction is multiplied by an integer, the value of H for that reaction must be multiplied by the same integer; *6 Elements in their standard states are not included in the o H reaction calculations. For an element in its standard state Hof is equal to zero. Units for enthalpy are kJ/mol Spontaneous processes and entropy A process is said to be spontaneous if it occurs without outside intervention. Spontaneous processes may be fast or slow. After many years of observation, scientists have concluded that the characteristic common to all spontaneous processes is an increase of property called entropy (S). What is entropy? *7 entropy can be viewed as a measure of randomness or disorder. Nature always moves toward the most probable state available to it. We can state this principle in terms of entropy:

6 In any spontaneous process there is always an increase in the entropy of the universe. This is the second law of thermodynamics. The total energy of the universe is constant (first law of thermodynamics), but the entropy is increasing. Suniv = Ssyst + Ssurr. To predict whether a given process will be spontaneous, we must know the sign of Suniv. If Suniv is positive, the entropy of the universe increases and the process is spontaneous in the direction written. If Suniv is negative, the process is spontaneous in the opposite direction. If Suniv is zero, the process has no tendency to occur and the system is at equilibrium. Absolute values for many thermodynamics characteristics of a system, such as enthalpy, can not be determined, but we can assign absolute entropy values. Consider a solid substance at 0 oK, where molecular motion virtually ceases. If the substance is a perfect crystal, its internal arrangement is absolutely regular. There is only one way to achieve this perfect order: every particle must be in its place. Thus a perfect crystal represents the lowest possible entropy. The entropy of a perfect crystal at 0 K is zero. This is a statement of the third law of thermodynamics. As the temperature of a perfect crystal increases, the entropy of the substance increases with the temperature too. Since S is zero for a perfect crystal at 0 K, the entropy value for the substance at a particular temperature can be calculated. A perfect crystal at 0 K is an unattainable ideal, taken as a standard but never actually observed. The standard entropy values (So) of many common substances at 298 K and 101,3 kPa are listed in a special tables. Units of S are J/mol.K ! Because entropy is a state function of the system, the entropy change for a given chemical reaction can be calculated by Hess s law: Soreaction = niSoprod - njSoreactants Free energy For chemical reactions we are often interested in the standard free energy change (Go); the change in free energy that will occur if the reactants in their standard states are converted to products in their standard states. There are several ways to calculate Go. One common method uses the equation Go = Ho TSo which applies to a reaction carried out at a constant temperature. Second method. Like enthalpy and entropy, free energy is a state function. We can use procedures for finding G similar to those for finding H and S using Hesss law.

7 Goreaction = niGof prod njGof react The standard free energy of formation ( Gof) of a substance is defined as the change in free energy that accompanies the formation of 1 mole of a substance from its constituent elements with all reactants and products in their standard states. The standard free energy of formation of an element in its standard state is zero. Units of Go are kJ/mol *8 When Go is equal to zero, the system is at an equilibrium with the products and reactants. *9 When Go is less than zero ( Go < 0) the forward reaction is spontaneous in the system. *10 When Go is greater than zero ( Go > 0) the reverse reaction is possible.

8 AQUEOUS SOLUTIONS When a mixture is homogeneous, it is called a solution. Solutions can be gases, liquids or solids. When the solvent is water, solutions are called aqueous solutions. Solution composition Because a solution, unlike a chemical compound, has a variable composition, the relative amounts of substances in a solution must be specified. The qualitative terms diluted (relatively little solute present) and concentrated (relatively large amount of solute present) are often used to describe solution content, but we need to define solutions composition more precisely. The most commonly used expression of concentrations is molar concentration (M). The molar concentration is defined as the number of moles of solute per volume of solution in litres. If we say - 1 M solution of substance - it means a solution containing 1 mole of substance (solute) per 1 litre of solution. Another way of describing solution composition is the mass percentage. Solutions of acids and bases The first person to recognize the essential nature of acids and bases was Svante Arrhenius. He postulated that acids produce hydrogen ions, while bases produce hydroxide ions. A more general definition of acids and bases is Br nsted-Lowry acidbase model: An acid is a proton (H+) donor and a base is a proton acceptor. H O +H H Cl H O H H
+

+ Cl

Note that the proton (H +) is transferred from the HCl molecule to the water molecule forming H3O+, which is called hydroxonium ion. The general reaction that occurs when an acid is dissolved in water can be represented as HA(aq) + H2O(l) H3O+(aq) + A (aq) (1) acid base conjugate acid conjugate base This representation emphasises the significant role of the polar water molecule in pulling the proton from the acid. Note that the conjugate base is everything that remains of the acid molecule after a proton is lost. The conjugate acid is formed when a proton

9 is transferred to the base. A conjugate acid-base pair consists of two substances related to each other by the donating and accepting of a single proton. It is important to note that equation (1) really represents a competition for the proton between the two bases H2O and A. If H2O is a much stronger base than A , that is, if H2O has much greater affinity for H+ than does A- , the equilibrium position will be far to the right. Most of the acids dissolved will be in ionized form. Conversely, if A is a much stronger base than H2O, the equilibrium position will be far to the left. In this case most of the acid dissolved will be present at equilibrium as HA. The equilibrium expression for the reaction given in equation (1) is
Ka

[ H O ] [ A ] = [ H ] [ A ] =
+ + 3

[ HA]

[ HA]

Ka is called the acid dissociation constant. Both H 3O+aq and H+aq are commonly used to represent the hydrated proton. We will often use simply H+, but you should remember that it is hydrated in aqueous solutions. In a dilute solution we can assume that concentration of liquid water remains essentially constant when an acid is dissolved. Thus the term [H2O] is not included in equation and the equilibrium expression has the same form as that for the simple dissociation: HA(aq) H+(aq) + A (aq) and
Ka =

[ H ] [ A ]
+

[ HA]

The strength of an acid is defined by the equilibrium position of its dissociation reaction (1) HA(aq) + H2O(l) H3O+(aq) + A (aq) (1) acid base conjugate acid conjugate base The stronger the acid, the weaker its conjugate base. The stronger the base, the weaker its conjugate acid Water as an acid and a base A substance is said to be amphoteric if it can behave either as an acid or as a base. Water is the most common amphoteric substance. We can see this clearly in the auto ionization of water, which involves the transfer of a proton from one water molecule to another to produce a hydroxide ion and a hydroxonium ion: H O + O H H O + O +

H H H H H In this reaction one water molecule acts as an acid by offering a proton, and the other acts as a base by accepting the proton. We can simply write this reaction as 2H2O(l) H3O+(aq) + OH (aq) and this reaction leads to the equilibrium expression Kw = [H3O+][OH-] or Kw = [H+][OH]

10 Kw is called the ion-product constant (or the dissociation constant) and always refers to the autoionization of water. Experiment shows that at 25 oC [H+] = [OH-] = 1,0 107 mol/l Which means that at 25 oC Kw = [H+][OH-] = 1,0 1014 mol2/l2 The units are customary omitted. It is important to recognize the meaning of Kw . In any aqueous solution at 25 oC, no matter what it contains, the product of [H+] and [OH] or ([H+] [OH-]) always equals 1,0 1014. There are three possible situations (at 25 oC): A neutral solution, where [H+] = [OH] An acidic solution, where [H+] > [OH] A basic solution, where [H+] < [OH] Sample exercises 1. Calculate [H+], if [OH] = 1,0 105 mol/l
10 [ H ] = 1,[0OH ]
+ 14

1,0 10 14 = 1,0 10 9 mol/l 5 1,0 10

Since, [OH] > [H+], the solution is basic. 2. Calculate [OH], if [H+] = 1,0 104 mol/l

OH =

1,0 10 14 = 1,0 10 10 mol/l 1,0 10 4

Since, [H+] > [OH], the solution is acidic. The pH scale Because [H+] in an aqueous solution is typically quite low, the pH scale provides a convenient way to represent solutions acidity. The pH is a log scale based on 10 where pH = - log [H+] + Thus for a solution where [H ] = 1.107 M, pH = 7 Similar log scale can be used for [OH] pOH = - log [OH] pKw = - log [H+][OH] = pH + pOH = 14 A neutral solution, 1.10
7

pH = 7; pH < 7; pH > 7;

[H+] = 1.107 [H+] > 1.107 [H+] < 1.107

pOH = 7 pOH > 7 pOH < 7

[OH] = [OH] < [OH] >

An acidic solution, 1.107 A basic solution, 1.107

Sample exercises. 1. Calculate pH, if [OH-] = 1.103 mol/l


,0 10 [H ] = 1 1,0 10
+ 14 3

= 1,0 10 11 mol/l

11 or pH = log 1,0 1011 = 11

pOH = log 1,0 103 = 3 pH = 14 pOH = 14 3 = 11 2. Calculate pH, if CNaOH = 0,001 mol/l [OH] = 1.103 1 1 = 1,0 103 mol/l pOH = 3; pH = 14 3 = 11

12 Acid-base properties of salts When a salt dissolves in water, we assume that it breaks up into its ions, which move about independently; at least in dilute solutions. Under certain conditions these ions can behave as acids or bases and water solutions of salts can be either acidic or basic (alkaline). Such salts are said to be hydrolyzed in water solution. Hydrolysis is a reaction between water and ions of dissolved salt. 1. Salts that produce neutral solutions. As mentioned before the conjugate base of a strong acid has virtually no affinity for protons as compared to that of the water molecule HCl + H2O H3O+ + Cl acid base c.acid c.base This is why strong acids completely dissociate in aqueous solutions. Thus, when anions from strong acids (such as Cl , NO3, SO42 etc.) are placed in water, they do not combine with H + and have no effect on the pH. Cations from strong bases (such as Na+, K+, Ba2+ etc.) have no affinity for H+ nor can they produce H +, and so they too have no effect on the pH of an aqueous solutions. Salts that consist of the cations of strong bases and the anions of strong acids have no effect on [H+] when dissolved in water. This means that aqueous solutions of salts such as KCl; NaCl; NaNO 3; KNO3 etc. are neutral (have a pH=7). We can say that in the case of such solutions there is no hydrolysis - there is no reaction between water and ions of dissolved salt. 2. Salts that produce basic solutions. In an aqueous solution of sodium acetate CH 3COONa, the main particles are: Na+, CH3COO and H2O. What are the acid-base properties of each component? The Na+ ion has neither acid nor base properties. The CH 3COO ion is the conjugate base of acetic acid - a weak acid. This means that CH 3COO has a significant affinity for a proton and is a base. Finally, water is a weakly amphoteric substance. The pH of this solution is determined by the CH 3COO ion. Since, CH3COO is a base, it will react with the best proton donor available. In this case, water is the only source of protons, and the reaction between the acetate ion and water is CH3COO(aq) + H2O(l) CH3COOH(aq) + OH(aq) base acid conj. acid conj. base Note that this reaction, which yields a basic solution, involves a base reaction with water to produce hydroxide ion and a conjugate acid. In general we can write B(aq) + H2O(l) BH+(aq) +OH (aq) base acid conj. acid conj. base Next example: Na2CO3 2Na+ + CO32 H2O CO32 + H2O HCO3 + OH base acid conj. acid conj. base

13 For any salt whose cation has neutral properties (such as Na +, K+ etc.) and whose anion is the conjugate base of a weak acid, the aqueous solution will be basic.

3. Salts that produce acidic solutions. Some salts produce acidic solutions when dissolved in water. For example, when solid NH4Cl is dissolved in water, NH4+, Cl ions and H2O molecules are present. NH4+ behaves as acid. The Cl ion has virtually no affinity for H+ in water and does not affect the pH of the solution NH4+ + H2O NH3 + H3O+ acid base conj. base conj. acid Salts of which the cation is the conjugate acid of a weak base, produce acidic solutions. A second type of salts that produce an acidic solution is one that contains a highly charged metal ion. For example, when solid aluminium chloride - AlCl 3 - is dissolved in water, the resulting solution is significantly acidic. The Al3+ ion is not itself a Br nsted - Lowry acid. But highly charged metal ions are hydrated in water solutions, which means that [Al(H2O)6]3+. The hydrated ion [Al(H2O)6]3+ formed in water is an acid. The high charge on the metal ion polarizes the O-H bonds in the attached water molecules, making the hydrogen atoms in these water molecules more acidic than those in free water molecules so [Al(H2O)6]3+ + H2O [Al(OH)(H2O)5]2+ + H3O+ acid base conj. base conj. acid or Al3+ + H2O Al(OH)2+ + H+ Typically, the higher the charge of the metal ion, the stronger the acidity of the hydrated ion. These cations may experience a secondary hydrolysis to a slight extent Al(OH)2+ + H2O Al(OH)2+ + H+ Al(OH)2+ + H2O Al(OH)3 + H+ and very small amount of salt is hydrolyzed accordingly these reactions. In general: salts of strong acids and weak bases form acidic solutions. 4. Salts which are formed from ions with neither basic nor acidic properties. Because the equilibrium system for these cases is quite complicated, we will consider only qualitative aspects of such problems. If salts are formed from cations of a weak base and anions of a weak acid, these salts will be hydrolyzed completely in water solutions. For instance: Al2S3 + 6H2O 2Al(OH)3 + 3H2S

14 In general: salts of weak acids and weak bases form solutions that may be neutral and in these solutions pH 7.

15 OXIDATION - REDUCTION REACTIONS Reactions, in which one or more electrons are transferred, are called oxidation - reduction reactions, or redox reactions. Or reactions in which elements undergo a change in oxidation number (state) are redox reactions. 0 +1 +2 0 Zn + 2 HCl ZnCl2 + H2 Zn0 2e Zn2+ 2H+ + 2e H2 Rules for assignation of oxidation states 1. The oxidation state of an atom in an element is 0. For example, Na, Cl2, H2 ... 2. The oxidation state of a mono atomic ion is the same as its charge. For example oxidation state of the Al3+ is +3. 3. Oxygen is assigned an oxidation state of 2 in its covalent compounds, such as CO, CO2, SO2, H2O ... The exception of this rule occurs in peroxides (compound contains O22- group), for example H2O2. 4. In its covalent compounds with non-metals hydrogen is assigned an oxidation state of +1. For example in compounds HCl, NH 3, H2O... 5. In binary compounds the element with the greater attraction for the electrons in the bond is assigned a negative oxidation state equal to its charge in its ionic compounds. 2 3 1 For example, H2S, NH3, HCl... 6. The sum of the oxidation states must be zero for an electrically neutral compound, for example +1+62 H2SO4 Total = 0 In some redox reactions the electron transfer occurs in a literal sense to form ions 0 0 +1 1 2 Na + Cl2 2 NaCl However, sometimes the electron transfer occurs in a more formal sense 1+1 0 +4 2 +1 2 CH4 + 2O2 CO2 + 2H2O With this background we can now define some important terms. Oxidation is an increase in oxidation state or a loss of electrons. Reduction is a decrease in oxidation state or a gain of electrons. 0 0 +1 1 2Na + Cl2 2NaCl

16 Sodium is oxidized and chlorine is reduced. In addition Cl 2 is called the oxidizing agent (electron acceptor) and Na is called the reducing agent (electron donor). An oxidizing agent is reduced and a reducing agent is oxidized in a redox reaction.

17 Oxidizing and reducing agents Reducing agents. 1. Metals in elementary state. Me ne Me+n 2. Hydrogen - H2 3. Metal ions with low charges if they can have a higher charges. Fe2+ e- Fe3+ 4. Non-metallic single anions. 2I 2e I20 5. In industry C, CO, H2 - active metals. Oxidizing agents. 1. Oxygen O2 2. Halogens F2, Cl2, Br2, I2 3. Metal ions with high charges. Sn 4+ + 2e- Sn2+ 4. Polyatomic anions in which the main element has the highest oxidation state. +7 MnO4 + 5e + 8H+ Mn2+ + 4H2O pH < 7 + MnO4 + 3e + 4H MnO2 + 2H2O pH 7 2 MnO4 + e MnO4 pH > 7 Balancing redox equations In using the oxidation states method to balance a redox equation, we find the coefficients for the reactants that will make the total increase in oxidation state and reactants that will make the total decrease in oxidation state. The remainder of the equation is then balanced by inspection. +7 +4 +2 +6 2KMnO4 + 5Na2SO3 + 3H2SO4 2MnSO4 + 5Na2SO4 + K2SO4 + 3H2O
oxidizing agent reducing agent

+7 +2 Mn + 5e Mn 2 +4 +6 S 2e S 5 The next problem is how to recognize whether a redox reaction is possible or not? The possibility of reaction realization depends on the value of electromotive force E of the redox reaction. E = Eooxidizing agent Eoreducing agent o E is standard redox potential of oxidizing or reducing agent. The unit of Eo is the volt. Redox reaction is possible when E > 0.

18

METAL CHEMICAL PROPERTIES Lets consider the reactions of metals with water, alkaline aqueous solutions, acids and salts in aqueous solutions, again emphasizing, that the metals in chemical transformations always behave as reducing agents. Me ne Men+ The reaction is thermodynamically possible if the Gibbs energy of the chemical process G < 0. Gibbs energy G with the redox process electromotive force is related to the equation: G = zFE, where z is the number of electrons which in the reaction move from the reducing agent to the oxidising agent.

F is Faraday's constant (96500 C / mol); E (EMF) is a redox process electromotive force. So reaction can take place, if G <0 and E> 0. Activity of metals in aqueous solutions is characterized by the metal redox potential. With its help, we can predict the possible redox reactions direction. Redox reaction is possible if the oxidizing agents redox potential is greater than the reducing agents redox potential E ox>Ered and reaction electromotive force E (EMF) is a positive value: E = Eox Ered > 0 Metal standard redox potential found in Fig. 2. (Metals activity series)

Fig. 2. Metals activity series

Other redox potential values are found in chemistry handbooks. 1. Metal reactions with water Metal reaction with water occurs when the hydrogen electrodes potential is greater than the metal electrodes potential. Hydrogen redox potential E 0 depends on the pH and at standard conditions (298 K, PH2 gas partial pressure of 101.3 kPa) the relationship is characterized by the equation: E = 0.059 pH (V) Under neutral conditions (pH = 7) hydrogen redox potential value is E = - 0.059 pH 0.059 x 7 = 0.41 V

19 So all metals whose redox potential value is less than - 0.41 V can react with water. The reaction takes place according to this equation: 2Me + 2HOH 2MeOH + H2 Examples: 2Na + 2H2O 2NaOH + H2 E = Eox Ered = 0.41 ( 2.71) = 2.30 V, E> 0 Ca + 2H2O Ca(OH)2 + H2 E = Eoks Ered = 0.41 ( 2.79) = 2.38 V, E> 0
E0 Na + / Na = 2.71 V

E0

Ca 2 / Ca

= 2.79 V

Based on the two metals redox potential values, the water should react faster to calcium and slower to sodium. In practice, however, sodium reacts with water much faster. This phenomenon occurs because the reaction takes place on the surface of the metal. Less soluble Ca(OH)2 layer prevents water access to the metal surface, as Ca (OH)2 solubility in water is significantly less than the solubility of NaOH. Pure aluminum and zinc normally do not react with water because Al(OH)3 and Zn(OH)2 (similar to the Be (OH)2, Pb(OH)2, Sn(OH)2, etc.) are insoluble in water compounds and prevent access of water to the surface of the metal. 2. Metal reactions with aqueous solutions of strong bases. Also in these solutions the reaction of metals with water takes place. In an alkaline medium (pH = 14) hydrogen redox potential value is E = V 0.059 pH 0.059 14 = 0.82 V If the metal is coated with a water-insoluble oxide layer (Al2O3, Cr2O3, ZnO, etc.) or reacting with water to form insoluble hydroxides such as Al(OH)3 and Zn(OH)2, then there is no reaction with water. Therefore, aluminum is widely used in electrical engineering as a good conductor, as a construction and building material and also in domestic applications, despite the fact that aluminum is an active metal: E0Al3+/Al = 1,66 V If metal oxides (Al2O3, etc.) and hydroxides ((Al(OH)3, etc.) are amphoteric compounds, they react with alkali to form soluble complex compounds such as: Al2O3 + 2NaOH + 3H2O 2Na[Al(OH)4] Al(OH)3 +NaOH Na[Al(OH)4] After removal of the metal surface layer of insoluble compounds aluminum quickly reacts with water : 2Al + 6H2O 2Al(OH)3 +3H2

20 After that insoluble Al(OH)3 forms soluble complex compound from the reaction of alkali: Al(OH)3 +NaOH Na[Al(OH)4] By summing up the two previous equations we obtain: 2Al + 6H2O 2Al(OH)3 + 3H2 2Al(OH)3 + 6NaOH 2 Na3[Al(OH)6] 2Al + 6NaOH + 6H2O 2Na3[Al(OH)6] + 3H2 This process results with aluminum very quickly reacting with alkaline aqueous solutions. Therefore, the aluminum must not be in contact with an alkaline aqueous solution. Similarly metals whose hydroxides are amphoteric (Al, Zn, Be, Sn, Pb) react with aqueous solutions of strong bases. However, these metals react much more slowly, because metals are less active: Zn + 2NaOH + 2H2O Na2[Zn(OH)4] + H2 3. Metal reactions with the acid aqueous solutions. We can classify all acids as acids where anions are non-oxidizing agents and acids where anions are oxidizing agents. Acids where anions are non-oxidizing agents a) In HCl, diluted H2SO4, CH3COOH, H3PO4, etc. aqueous solutions H3O+ ions act as an oxidizing agent. It is assumed that in acidic solutions hydrogen redox potential E0 = 0.00 when in fact it depends on the pH of the solution. So in theory these solutions may react with metals which redox potential has a negative value. In these cases the oxidizing agent is H + (H3O)+ and metals whose electrode potentials are less than 0.00 V can react with these acids. These reactions form salt and hydrogen. For example: Zn + 2HCl ZnCl2 + H2 Zn 2e Zn2+ 2H+ + 2e H2 Reactions like this are possible only with metals that are more active then H+ It should be noted that in these reactions the solubility of the reaction product may substantially affect the reaction process. Example: E0 Pb + H2SO4 PbSO4 + H2 2 H 3 O + / H 2 + 2 H 2 O = 0 V; E = Eox Ered = 0 ( 0,13) = 0,13 V;

E0 Pb 2 + / Pb = 0,13 V

E>0

21 In this reaction Eox> Ered and the reaction is possible. However, the insoluble PbSO4 layer prevents acid to access the surface of the metal, and this reaction is practically nonexistent. Therefore, the lead can be used for lead battery manufacturing. Lead reacts with acetic acid: Pb + 2CH3COOH Pb(CH3COO)2 + H2 Although acetic acid is much weaker than H2SO4 and HCl, lead will react faster because the reaction product Pb(CH3COO)2 is a soluble compound. Metal reactions with acids where anions are oxidizing agents Such acid (H2SO4 conc., HNO3 conc., HNO3 dil.) anions are stronger oxidizing agents than H3O+ ions. Metal ions and various anion reduction products are formed in these reactions. In reactions with concentrated H2SO4, SO2, S, or H2S may be formed from the SO42- ion, with oxidation states of the sulfur being +4, 0 and -2 respectively. (Trace amounts of hydrogen may also be released in these reactions ). It should be noted that all three compounds will be the reaction products. Which of these SO42- reduction products is formed depends on several factors: the metal electrode potential (metal activity), temperature, and acid concentration. The predominantly formed compound should be written in the reaction equation. 2The possible SO4 ion redox equations are: SO42- + 2e + 4H3O+ SO42- + 6e + 8H3O+ SO42- + 8e + 10H3O+ SO2 + 6H2O S + 12H2O H2S + 14H2O Eo = +0,17 V Eo = +0 36 V Eo = +0,31 V

The more negative electrode potential of a metal is (metal is more active), the lower the oxidation states of the acid reduction products are. Example: Cu + 2H2SO4 conc CuSO4 + SO2 + H2O Reaction is carried out by heating 3Zn + 4H2SO4 conc 3ZnSO4 + S + 4H2O Reaction is carried out by heating 4Mg + 5H2SO4 conc 4MgSO4 + H2S +4H2O Responding to (50%) acid. It should be noted that cold concentrated sulfuric acid passivate Al, Fe, Ni, Cr, stimulating the formation of oxide layers. For example, railway tanks and barrels for storage and transportation of concentrated sulfuric acid are made of steel. In reactions with concentrated and diluted HNO3, NO2, NO, N2O, N2 and NH4+ can form with oxidation states of the nitrogen being +4, +2, +1, 0, and 3 respectively. In these reactions, as well in reactions with concentrated sulfuric acid, hydrogen is also released but in very small amounts only. The following NO3 ion redox equations are possible:

22 NO3 + 2H+ +e NO3 + 4H+ +3e 2NO3 + 10H+ + 8e 2NO3 + 12H+ +10e NO3 +10H+ + 8e NO2 + H2O NO + 2H2O N2O + 5H2O N2 + 6H2O NH4+ + 3H2O Eo = +0,80V Eo = +0,96 V Eo = +1,12 V Eo = +1,24 V Eo = +0,87 V

So metal reaction with HNO3 products are salt, water and the predominant possible reduction product (as in reactions with sulfuric acid, a mixture is usually formed). Similarly the predominantly formed compound should be written in the reaction equation.

Nitrogen compounds with mainly higher oxidation states are formed when using more concentrated nitric acid and less-active metals, lower oxidation states - with more active metals and more diluted nitric acid, but in all other cases - the average oxidation states.The table below identifies the main reaction products of concentrated and diluted nitric acid with metals of different activities. Metals and nitric acid reaction products Concentrated HNO3 1) Al, Cr, Fe, Ni, Au, Pt, Ir, Ta 2) Inactive metals: Cu, Ag, In, Pb etc. 3) Active metals: Li, Na, K, Ca etc. Nonreacting NO2 N2O NO

Diluted HNO3

1) Inactive metals: Cu, Ag 2) Active metals: Li, Na, K, Ca, Mg, NH4NO3 Zn un Fe

Examples: Concentrated H2SO4; HNO3 reacts with all metals, (except Au and Pt) Cu + 2H2SO4 conc CuSO4 + SO2 + H2O 0 Cu 2e Cu2+ +6 +4 S + 2e S Sulphur of H2SO4 is reduced by metal copper. Cu + 4HNO3 conc Cu(NO3)2 + 2NO2 + 2H2O 0 Cu 2e Cu2+ +5 +4 N+e N Nitrogen of nitric acid is reduced by metal copper.

23 When we use diluted HNO3 , metals react as follows: 3Cu + 8HNO3 diluted 3Cu(NO3)2 + 2NO + 4H2O 0 Cu 2e Cu2+ 3 +5 +2 N + 3e N 2 If the nitric acid (HNO3) is very diluted and the metal is very active, the reaction is as follows: 4Mg + 10HNO3 4Mg(NO3)2 + NH4NO3 + 3H2O 0 Mg 2e Mg2+ 4 +5 3 N + 8e N 1 In concentrated H2SO4 and HNO3 some metals (Fe, Ni, Cr, Al) become passive - they dont react. 4. Metal reactions with the aqueous solutions of salts. The aqueous solutions of salts must be considered as complex systems where a number of processes might be possible. a) A solution of salts contains metal cations, that may be strong enough oxidizing agents to oxidize metals that are more active than the cations, such as Zn + CuSO4 Cu + ZnSO4
0 0 The condition for this reaction to be true is Eox > Ered, or E Cu 2+ / Cu > E Zn 2+ / Zn . If this condition is not fulfilled the reaction does not occur.

b) Some of the salt anion is hydrolysed resulting in the pH of the solution being different from the neutral pH, when acid or alkaline environment is formed (solution contains H3O+ or OH ions). c) The metal can react with acids or bases, that have been formed as a result of hydrolysis. Examples: Mg + ZnCl2 + H2O ?

a) Zinc ions can oxidize magnesium because

E 0 Zn

2+

/ Zn

> E 0 Mg

2+

/ Mg

Mg + Zn2+ Mg2+ + Zn Mg + ZnCl2 MgCl2 + Zn Reaction is possible because E > 0: E = ( 0.76 (2.38) = 1.62 V

24 b) Zinc ions are hydrolysed, creating an acidic environment: Zn2+ + H2O ZnOH+ + H3O+;

c) Magnesium reacts with product of hydrolysis H3O+: Mg + 2 H3O+ Mg2+ + 2H2O + H2. a) Fe + AlCl3 + H2O ?
3+

0 Aluminum ions cant oxidize iron because E Al

/ Al

< E Fe
0

2+

/ Fe

Reaction is not possible because E < 0:

E = ( 1.66 (0.47) = 1.19 V

b) Aluminum ions are hydrolysed, creating an acidic environment: Al3+ + 2H2O AlOH2+ + H3O+;

c) Iron reacts with product of hydrolysis H3O+: Fe + 2 H3O+ Fe2+ + 2H2O + H2. a) Cd + Cu(NO3)2 + H2O ?

Copper ions can oxidize cadmium because

E 0 Cu

2+

/ Cu

> E 0Cd

2+

/ Cd

Reaction is possible because E > 0:

E = +0.34 (0.40) = + 0.74V

b) Copper ions are hydrolysed, creating an acidic environment: Cu2+ + 2H2O CuOH+ + H3O+;

(in solution forms diluted HNO3) c) Cadmium reacts with product of hydrolysis - diluted HNO3: 3 Cd + 8HNO3 3Cd(NO3)2 + 2NO + 4H2O a) Fe + CaCl2 + H2O ?
E
0 Ca 2+ / Ca

Calcium ions cant oxidize iron because

<

E 0 2+ Fe / Fe

Reaction is not possible because E < 0: b) Calcium ions are not hydrolysed. c)

E = 2.79 (0.47) = 2.32V

Iron does not react with calcium chloride solution.

Al + Na2CO3 + H2O ?

25

a)

Sodium ions cant oxidize aluminium because Reaction is not possible because E< 0:

E 0 Na + / Na < E 0 Al3+ / Al
E = 2.71 (1.66) =

1.05V b) Carbonate ions are hydrolysed, creating a basic environment: CO32 + HOH HCO3 + OH (in solution forms NaOH) c) Aluminum reacts with product of hydrolysis - solution of NaOH: 2Al + 6NaOH + 6H2O 2Na3[Al(OH)6] + 3H2

26 ELECTROCHEMISTRY Electrochemistry is defined as the study of the interchange of chemical and electrical energy. It is primarily concerned with two processes that involve redox-reactions: the generation of an electric current from a chemical reaction (galvanic cell), and the opposite process - the use of a current to produce chemical change (electrolysis). Galvanic cells and cells potential To understand how a redox reaction can be used to generate a current, lets consider the reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) reducing oxidizing agent agent It is useful to break a redox reaction into half-reactions, one involving oxidation, one involving reduction. Zn 2e Zn2+ Cu2+ + 2e Cu When the reaction between Zn and 2+ Cu occurs in solution, the electrons are transferred directly when the reactants collide. Thus no useful work is obtained from the chemical energy involved in the reaction. How can we harness this energy? The key is to separate physically the oxidizing agent and the reducing agent, thus requiring the electron transfer to occur through a wire. When we construct such apparatus, no flow of electrons occurs (Fig. 3). Why? We can solve this problem very Fig. 3. Galvanic cell without salt bridge simply. The solutions must be connected (without allowing the two solutions to mix) so that ions can also flow to keep the net charge in each compartment zero. This can be accomplished by using a salt bridge (U - tube filled with an electrolyte) or a porous partition in a tube connecting the two solutions (Fig. 4). Galvanic cell is a device in which chemical energy is changed to electrical energy. The oxidation and reduction reaction in an electrochemical cell occurs at the interface between the electrode and the solution where the electron transfer occurs. The electrode at which oxidation occurs is called the anode; the electrode at which reduction occurs is called the cathode. Fig. 4. Galvanic cell with salt bridge () A Zn 2e Zn2+ (+) K Cu2+ + 2e Cu

27 Zn + Cu2+ Zn2+ + Cu () A Zn ZnSO4 CuSO4 Cu K (+) A galvanic cell consists of an oxidizing agent in one compartment with the power to pull electrons through a wire from a reducing agent in the other compartment. The driving force of the electrons is called the cell potential or the electromotive force of the (E). The unit is the volt (V). In our case galvanic cell (Zn ZnSO4 CuSO4 Cu) is usually called the Voltaic cell or Galvani cell (After a name of two Italians Volta & Galvani). A Voltaic cell consists of two metal electrodes, each in contact with a solution of its ions. Each of these compartments is called a half-cell. The reaction taking place at each electrode is called a half-reaction. The potential difference between an electrode and its solution in a halfreaction is known as its electrode potential (E). The cell potential is found by mathematics as follows E = Ecathode Eanode The potential difference across Voltaic cell is easily measured. However there is no way to measure an individual electrode potential. The electrode potential of a half-reaction can be determined by using a standard half-cell along with it as a reference electrode. Relative to this potential, a specific potential can be determined for the other electrode of the complete cell. Chemists use a hydrogen electrode immersed in a molar (M) solution of H+ ions as a standard reference electrode. This practice provides a convenient way to examine the relative tendencies of metals to react with aqueous hydrogen ions. It is responsible for the metals of activity series listed in a special table. The hydrogen electrode consists of a platinum electrode dipping into an acid solution of 1 M concentration and surrounded by hydrogen gas at 1 atmosphere (101,3 kPa) pressure. This standard hydrogen electrode is assigned a potential of zero volts. The half-cell reaction is H2(g) 2e 2H+(aq) Therefore, the potential difference across the complete cell is attributed entirely to the electrode of the other half-cell. Suppose we construct a complete cell consisting of zinc half-cell where zinc concentration is 1 M and a standard hydrogen half-cell (Fig. 5). The potential difference across the cell measures the electrode potential of the zinc Fig. 5. Zinc hydrogen galvanic cell electrode relative to the 0 0 hydrogen electrode ( E 2 H + / H 2 = 0 V). The E Zn 2+ / Zn is found to be 0.76 V.

28 The standard electrode potential, E o, of an electrode is given a negative value if this electrode has a negative charge relative to the standard hydrogen electrode. The standard electrode potential, E o, of an electrode is given a positive value if this electrode has a positive charge relative to the standard hydrogen electrode.

29 For Galvani element given above we can write the following scheme: A () Zn Zn2+ H+ H2 (Pt) (+) K A () Zn 2e- Zn2+ K (+) 2H+ + 2e H2 Zn + 2H+ Zn2+ + H2 or Zn + H2SO4 ZnSO4 + H2 o o E = E cathode Eoanode = 0 ( 0.76) = 0.76 V The Nernst equation The real electrode potential depends on the concentration of metal ions in the electrolyte. The relationship between the electrode potential and the concentrations of the half-cell components is given by equation, which commonly is called the Nernst equation after German chemist Hermann Nernst: E = E o +
0,058 log C Mez + , where z

E - electrode potential; Eo - standard electrode potential; z - number of electrons taking place in half-cell reaction; C - concentration of metal ions mol/l For example, A () Zn Zn2+ H+ H2 (Pt) (+) K CZn2+ = 0.1 mol/l EoZn/Zn2+ = 0.76 V Cag+ = 0.001 mol/l EoAg+/Ag = + 0.80 V

EZn/Zn2+ = 0.76 + 0.058/2 log 101 = 0.789 (V) EAg+/Ag = 0.80 + 0.058/2 log 103 = 0.713 (V) E = 0.713 ( 0.789) = 1.502 (V)

30 METAL CORROSION AND CORROSION PREVENTION The term corrosion applies to a number of processes whereby a metal changes as a result of interaction with its environment. Based on the kind of interaction the corrosion is categorised as chemical or electrochemical corrosion. Chemical corrosion includes the interaction of a metal with gases (O 2, N2, CO2, SO2 etc.) at high temperatures or corrosion in media that doesnt conduct electricity (in oil, gasoline). As a result of chemical corrosion a layer of oxides and salts is formed on the surface of the metal, which offers a greater or lesser degree of protection depending on its adhesion and porosity (Fig.6). In some cases there is a rapid production of a tough adherent film of oxide (Al 2O3, Cr2O3, ZnO, MnO) which protects the metal from further attack, halting the corrosion. Exposure of steel to high temperatures (however below 572 oC) results in a pronounced resistance to atmospheric corrosion due to the formation of oxide film Fe3O4 (FeO.Fe2O3). To test this you can apply a drop of copper (II) sulphate solution to two steel plates one with and one without the heat treatment. The reaction CuSO4 + Fe Cu + FeSO4 is faster on the heat-untreated steel plate and reddish spots of metallic copper appear faster. Electrochemical corrosion is interaction Fig.6. Scheme of of metal with a corrosion medium chemical (electrolyte) when metal oxidation and corrosion corrosion medium reduction does not occur in one stage but in a sequence of reactions involving the liberation, transfer and consumption of electrons that result in small but definite electrical currents flowing from one site to another. The rate of corrosion reaction depends on the value of metal electrode potential. Electrochemical processes resemble the processes in the galvanic cell. All metals in common use contain other metals or the admixture of them and being exposed to a potentially corrosive environment (electrolyte) their different reactivity creates an electrochemical cell Fig.7. The more active metal Me1 with a more negative value of potential E 1 becomes anode of the galvanic cell. Metal is ionized forming electrons (e) and ions (Mez+) A() Me1 ze + Me1z+ Electrons transfer to the less active metal Me2 with a more positive value of potential where they are consumed by oxygen (in neutral or basic circumstances). Fig.7. Scheme of electrochemical K (+) O2 + 2H2O + 4e 4OHcorrosion in neutral medium Positively charged metal ions migrate toward the cathode but the negatively

31 charged ions - toward the anode. Ions combine and the corrosion product is formed Me1z+ + zOH Me1(OH)z To be sure that the formation of electrochemical cell affects the rate of corrosion lets look at the following experiment. If a bit of zinc is placed in an acid (pH<7) it can be observed that hydrogen is released slowly due to the formation of a double electric layer on the surface of zinc (Fig. 7.) where positively charged zinc ions screen the zinc surface and impede approach and discharge of hydrogen ions. 2H+ + 2e 2H H2 If we touch the surface of zinc (E Zn2+/Zn = 0.76 V) with a copper wire (ECu2+/Cu = 0.34 V) (Fig. 9.) electrons transfer from zinc to copper. Discharge of hydrogen ions happens on the wire and the rate of hydrogen release increases. Transfer of electrons from the surface of zinc disturbs the original equilibrium in the double electric layer and new zinc ions diffuse into the solution.

Acid

Fig. 9. Action of galvanic cell A () Zn H+ Cu+ To renew equilibrium the fresh zinc (+) K ions move into the solution and the corrosion rate increases. In this case a short circuited galvanic cell is formed A ( ) Zn H+ Cu+ (+) K where the following half-reactions take place at the anode () Zn Zn2+ + 2e+ at the cathode (+) 2H + 2e 2H H2 (discharge of hydrogen) The overall reaction is Zn + 2H+ Zn2+ + H2 Technical zinc, if it contains a less active metal admixture, corrodes in the same way.

Fig. 8. Formation of a double electric layer on the surface of zinc

32 When the corrosion galvanic cell appears in a neutral medium (pH=7) atmospheric oxygen serves as a discharger at the cathode.

O2 O2
OH-

Droplet of water

O2
OHe-

Fe2+ e-

Fe2+

O2 K(+ )

K(+ )

A()

IRON Fig. 10. Corrosion of steel structure under the droplet of electrolyte In such corrosion galvanic cell (Fig.10) A ( ) Fe H2O, O2 Fe + O2 (+) K the following reactions occur: at the anode 2Fe 2Fe2+ + 4e at the cathode O 2 + 2H2O + 4e 4OH (discharge of oxygen) The overall reaction is 2Fe + O2 + 2H2O 2Fe2+ + 4OH The ions diffuse together and combine 2Fe2+ + 4OH Fe(OH)2 Iron (II) hydroxide can be oxidized by atmospheric oxygen: 4Fe(OH)2 + O2 + H2O 4Fe(OH)3 Thus the rusting of steel in a damp atmosphere involves a conversion of metallic iron to a mixture of oxides and hydroxides. The composition of rust can be xFeO . yFe2O3 . nH2O When two different metals which are in electrical contact are exposed to a potentially corrosive environment their different reactivity creates an electrochemical cell where the more active metal is oxidized at the anode, the reaction at the cathode in an acidic medium is the reduction of hydrogen ions to hydrogen gas but in a neutral medium (pH=7) - the reduction of oxygen gas and hydroxide ion formation. In such corrosion galvanic cell the following reactions occur: at the anode the more active metal is oxidized; at the cathode in a neutral medium (pH=7) atmospheric oxygen is reduced: O2 + 2H2O + 4e 4OH in acidic medium (pH<7) hydrogen ions are reduced:

33 2H+ + 2e 2H H2 If the metal is in contact with the salt solution the presence of some salts (CuSO4, ZnCl2, AlCl3, Pb(NO3)2, Na2CO3 etc.) triggers corrosion for the following reasons: 1) they may cause substitution reaction creating a metal with a more positive value of electrode potential and forms a corrosion galvanic cell; 2) as a result of salt hydrolysis corrosion medium becomes alkaline or acidic. For example, the following reactions take place with zinc in an aqueous solution of aluminium sulphate. It releases hydrogen gas: Al3+ + HOH AlOH2+ + H+ Zn + 2H+ Zn2+ + H2 Chloride and bromide ions (Cl, Br) are known to have great effect upon the corrosion rate. They are absorbed on the metal surface and the value of metal electrode potential decreases. Therefore the voltage of corrosion galvanic cell and the corrosion rate increases. To prevent corrosion metals are often coated with a more resistant metal or its alloy. Zinc and tin are used extensively as a protector on steel. If coating is not damaged the protective structure corrodes at the same rate as the coating itself. When the coating is damaged and the surface of the structure becomes unprotected, a corrosion galvanic cell is created where anod e cathod e anode Fig. 11. Corrosion of iron with zinc and tin coatings the more active metal becomes an anode. () Zn H+ Fe (+) and () Fe H+ Sn (+) or (pH>7) Zinc provides anodic protection for steel, preventing steel corrosion even when protection is damaged, whereas damaged tin protection (cathodic protection) accelerates the steel corrosion because of forming corrosion galvanic cell where steel is an anode. Sometimes to prevent corrosion of the structure, its connected to a more active metal than the one it is made of. For example, when a piece of lead is placed in acetic acid the following reaction occurs: 2Pb + 4CH3COO + O2 Pb2+ + 4CH3COO + 2H2O By adding potassium iodide yellow lead (II) iodide precipitate settles out of solution: Pb2+ 2I PbI2 (yellow precipitate) () Zn O2, H2O Fe (+) and (pH<7) cathod e

( ) Fe O2, H2O Sn (+)

34 If lead is put in contact with zinc under the same conditions it doesnt form lead (II) ions. In this case corrosion galvanic cell is created ( ) Zn H+ Pb (+) where anode is the more active zinc. So zinc becomes the protector of lead and yellow PbI 2 doesnt settle out from solution after KI has been added. The following reactions occur: at the anode Zn Zn2+ + 2e at the cathode (Pb) 2H+ +2e H2 To prevent corrosion metals widely is used cathodic protection (Fig. 12) which is a technique to control the corrosion of a metal surface by making it the cathode of a corrosion galvanic cell. The simplest method is by connecting the metal to be protected with a piece of another Fig.12. Cathodic protection: 1 - Pipeline; 2 anode. more easily corroded sacrificial -Sacrificial metal to act as the anode of the galvanic cell. Then instead of the protected metal the sacrificial metal corrodes. Cathodic protection systems are used to protect a wide range of metallic structures in various environments. Common applications are: steel water or fuel pipelines and storage tanks such as home water heaters, ship and boat hulls, Fig.13. Impressed current systems: 1 Pipeline; offshore oil platforms etc. 2 - Cathodic protection rectifier; 3 For larger structures, for Anode. example in long pipelines, galvanic anodes cannot economically deliver enough current to provide complete protection. For these structures an external direct current (DC) electrical power source is sometimes used to provide current (Fig. 13). Usually as DC power source will be cathodic protection rectifier, which converts alternating current (AC) power supply to a DC output.

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