Chemical Reactions 4.1 Introduction Biochemical and chemical reactions are vital to living organisms. For example, complex molecules such as starch or proteins have to be bro- en down into simpler molecules. These simpler molecules can then either be consumed in further biochemical reactions to produce energy ‘or used as building blocks to construct the complex molecules organ- {sms need for growth, repair, and reproduction. In fact, all the processes ‘of metabolism involve biochemical and chemical reactions, and so knowledge of how such reactions work is necessary for the understand- ing of living organisms. 4.2 Rates of Reaction ‘The speed of biochemical reactions can vary enormously. Some bio- ‘chemical reactions, such as muscle contraction, take place in thousandths of seconds, whereas others, such as the enzymic degradation of wood, an take years or decades to complete. For living organisms, the rate of reactions is extremely important. The smooth running of an organism's metabolism requires that reactions always go at an optimum rate. 4.3. Factors Affecting Rate of Reaction Reactions between molecules can occur only when molecules collide. If the collision is sufficiently energetic, bonds can be broken and then reformed in a different arrangement. The molecules that exist originally fnd take part in the reaction are termed the reactants, The molecules that result after a reaction has taken place are termed the products. “Three factors are important in controlling the rae of a reaction: |. Temperature—Temperature affects the speed at which molecules ‘move: the higher the temperature, the greater is the average speed of molecules. Therefore, as the temperature increases, collisions between molecules become more violent, This increases the chances of a reaction occurring. This topic is dealt with in greater depth in Chapter 16. 2. Catalysis—A catalyst is a substance that increases (or some- times decreases) the rate of a reaction while not itself being chemically changed at the end of the reaction. In biological systems, catalysis is brought about by enzymes. All reactions in living things are controlled by enzymes. This topic is covered in greater depth in Chapter 16. 3, Concentration—The higher the concentration of a reactant ina mixture, the greater is the number of collisions that molecules of that substance will undergo. in a given time. The greater Chemical reactions can vary enormously in rate, Enzymes contol the ates of Teactions in ving organisms. Chemical reactions ean occur ‘only when malecuies cle. Increasing the temperature wil always ineroase tho rate of & reaction Increasing the concentration of reactans offen increases the fate ofa reaction.Fate equations show how the rate oa reaction depends onthe ‘concentration of reactants Pitng the diferent graphs to find the one that gies a straight line enables us to determine the rd ofa feaction, number of collisions leads to a faster rate of reaction. In this chapter, we examine the role of concentration in determining the rate of reaction. 44 Rate Equations For a general reaction such as; A+B3C+D ‘A and B are termed the reactants, and C and D are called the product. tis commonly found that, at a fixed temperature and with a constant amount of catalyst present, the initial rate of reaction (ic. the speed at ‘which reactants are turned into products) can be modelled by an equa- tion such as Rate ‘KAT IBY an where k is a constant called the rate constant, [A] and [B] are the con- centrations of reactants A and B (in mol dir) and the powers to which their concentrations are raised, and x and y are chosen to match the observed rate of reaction, The powers x and y are called the orders of reaction with respect to reactants A and B, respectively. They are usually small whole numbers such as 0, 1, or 2. The overall order of reaction is given by x+y. The minus sign in Equation 4.1 indicates that as time goes on, the conicentfation of reactants goes down, 4.5 Integrated Forms of Rate Equations ‘The rate equation (Equation 4.1; called the differential form of the rate equation) allows us to calculate the rate of a reaction at any time pro ‘vided we know the concentrations of the reactants at that time and the rate constant, Often, we can measure the concentration of a reactant fairly easily but do not know the rate constant and so cannot use this equation. Using calculus, it is possible to integrate the rate equation to obiain an equation from which we can calculate the rate constant. ‘We can then use this knowledge to calculate either the rate of reaction expected with a given concentration of reactants or the concentration of reactants left after the reaction has proceeded for a given time. ‘The result ofthe integration depends on the order of the reaction. The derivations of the integrated rate equations for zero first, and second order reactions are found in the Appendix. In the following sections. the integrated rate equations are presented and graphical methods of determining rate constants explained. 4.6 Zero-Order Reactions In a zero-order reaction, the power to which the concentrations of the reactants are raised is zero for all reactants, Any number raised to the ‘power zero is equal to 1, so in this case, the rate of the reaction does not Chemistry for Life Sciencesdepend at all on the concentration of the reactants. The rate equation for such a reaction is: : Rate =-k an Zero-otder reactions are commonly found in cases where catalysis is “occurring. If there are lots of reactant molecules present, the catalyst is ‘working as fast as it possibly can—as soon as one reactant molecule has interacted with the catalyst, another one takes its place. Increasing con ‘centration of the reactant cannot inerease the rate of the reaction because the catalyst cannot work any faster. The catalyst is said to be saturated. ; 4.7 Integrated Form of the Zero-Order Rate Equation ‘The zero-order rate equation can be integrated to give: [AL = Al — kt 43) ‘where [Alp and [Al are the concentrations of A at the start of the reac tion and after a time ¢ has elapsed, respectively. ‘The integrated form of the rate equation is usually used to determine the rate constant of a reaction. If we can monitor the concentration of A by some means (for example, by taking samples for analysis at various intervals), then we can plot a graph of [A], versus ¢. This graph will give ‘a straight line of gradient equal to -k and y-intercept [Aly- 48. First-Order Reactions Ina first-order reaction, the rate at which the reaction goes depends on the concentration of only a single reactant. There may be more than one ‘reactant taking part in the reaction, but only one influences the rate of ‘reaction. The rate equation for such a reaction is Rate =-K(A] 44) “The reaction is first order with respect to A, and the order with respect ‘wall reactants is zero. The reaction is thus also first order overall. 'As we vary the concentration of A, the rate of reaction will change. For ‘example, if we double the concentration of A from [Al, to [Al,, 0 that [AhL=21Ah, rate of reaction becomes Rate=k(Aly = 2k(Al, ‘ate of reaction therefore doubles when the concentration of A doubles. “The Integrated Form of the First-Order Rate Equation reaction proceeds, A is used up and so its concentration falls. “sate of the reaction therefore slows as the reaction goes on. The Reactions ‘The rate of a zero-order reaction Is indopendent ofthe reactant Graph of A] versus time for zor0-order reaction. Integrated rate equations allow lu to determine rate constants. “The rate ofa tstorder reaction Is affected by the concentration cof only one reactant aconcentration of A at any time during the reaction can be represented by using the integrated form of the rate equation: InfA,=InfAlg— kt 45) where Inrepresents natural logarithm, [A], and [A], are the concentrations of Gephotin[Alversustime tora A at the start of the reaction and after a time r has elapsed, respectively. a In the case, we plot a graph of In{A], versus f to obtain a straight line of gradient -K and intercept In{A\}y 4.10 Second-Order Reactions “The rate ofa second-order Second-order reactions can be of two types, as described below: reaction may depend on the Concentration of either one oF ‘wo reactants. 4.10.1 Type 1 ‘The rate of the reaction depends on the concentration of only one reac- tant, The rate equation is: Rat -KIAP 46) ‘As we vary the concentrations of A, the rate of reaction will change but in a different way from that seen with first-order reactions. For example, if we double the concentration of A from [A], to [Al;, so that: (Ah=21Al, then the new rate of reaction will be giyen by Rate = -KIA] KQLAL,? —4K(A], ‘The rate of reaction therefore increases fourfold when the concentration of A is doubled. 4.10.2 Type? ‘The rate of reaction depends on the concentrations of two reactants. The rate equation is: Rate = -k{AJ[B] an Inthis case, doubling the concentration of either A or B will double the rate of reaction, Doubling both concentrations will increase the rate fourfold. 4.11 Integrated Forms of Second-Order Rate Equations 4111 Typel Equation 4.6 can be integrated to give: Ltt tl tl “8 48. Chemistry for Life Scienceswhere (A]and [A], are the concentrations of A at the start ofthe reaction and after a time t has elapsed, respectively 1 Plotting a araph of FAT. versus wl give a straight fine of gradient Bed ieee re 4112 Type? This rate Equation 4.7 can be integrated to give: 1 [LA Cl-BD "(Ly where [A] and [B], are the concentrations of A and B at the start of the reaction and [A], and [B}, are the concentrations of A and B after a time ¢ has elapsed, respectively. To obtain a straight-line graph of gradient k from this equation, we would have to plot a graph of the left-hand side of the equation versus t. This would require us to know both (Al, and [B], Its likely to be difficult to obtain simultaneous measurements of the Concentrations of two reactants, so a different approach is employed, 49) 4.12 Pseudo-First-Order Reactions : Any reaction the rate of which depends on more than one reactant can be transformed into a pseudo-first-order reaction. In the case of Type 2 second-order reactions, this can be done by having one of the reactants present in large excess. Suppose that we make the concentration of reac- tant B much larger than the concentration of reactant A. Then, when all of has reacted, the concentration of B will hardly have changed atall. We have, for the rate Equation 4.7: Rate = -K{AJ[B] [fBis present in such a large excess that its concentration hardly changes during the course of the reaction, then B is essentially constant (ie, {Blp= (Bl). The rate equation can then be written as follows: Rate = ~CA] where the new constant C = k[B]. The equation now has the same form as that of a first-order reaction, It can be integrated similarly to give: In{Al= Inf], -Ct 4.10) A graph of Inf versus will give a straight lin of gradient ~C=-K{B, from which k can be calculated if we know the original concentration of B. Chemical Reactions a3 j Graph of 14] versus time fora second-order reaction, Second-order reactions can be made into psoudo-fret-order reactions by having one reactant Present in high concentration 494.13. Reversible Reactions ‘The reactions we have considered so far have been unidirectional (that js, reactants have been transformed into products in a one-way process). ‘However, in many cases, it is found that the products of a reaction can Chemistry for Life Sciencesalso react together to regenerate reactants. Such a reaction is said to be reversible and is written with a double-headed arrow: A+B=C4+D 4414 Equilibrium If we start off such a reaction by mixing reactant A with reactant B, they start to react to form C and D. At first, only the forward reaction can occur, because no C or D has yet been produced, but as C and D begin to accumulate, they begin to react together to produce A and B. As A and B react, their concentration decreases, and so the rate of the forward reaction slows down. Conversely, as C and D are produced, their concentration increases and the rate of the backward reaction increases. This continues until the rates of the forward and backward reactions become equal. At this stage, the reaction is said to be in equilibrium. A and B continue to react together to form C and D, but € and D are now reacting at an equal rate to produce A and B. ‘The rate of the forward reaction is given by a rate equation of the following form: Rate(f) = k[AI[B] where Rate(f) is the rate of the forward reaction, k; is the rate constant of the forward reaction, and [A] and [B] are the concentrations of A and B, respectively. The rate ofthe backward reaction is given by a similar rate equation: Rate(b) = kICID] ‘where Rate(b) is the rate of the backward reaction, kis the rate constant for the backward reaction, and [C] and [D] are the concentrations of Cand D, respectively. ‘When the reaction has reached equilibrium, the forward and back- ‘ward rates are equal: K,(AIIB) = k(CHD] Rearranging this, we obtain: {e}[>] [J] ‘The left-hand side of this equation is formed from two constants and therefore must be constant. Because this constant is equal to the right- ‘band side, the right-hand side must also be a constant. This constant is ‘called the equilibrium constant, Ky for this reaction fe) _[e] [>] Ta a2) Tea ais) ‘Note that uppercase letters are used for equilibrium constants, and lower- ‘case letters are used for rate constants. = (un iz ay ‘Chemical Reactions SI‘The larger the equilibrium constant, the further the reaction goes in the forward direction. If the equilibrium constant is greater than about 50, the equilibrium lies far to the right, and it can be said that the ‘reaction goes to completion. If the equilibrium constant is smaller than bout 0.02, the equilibrium lies fart the left, and itcan be said that the reaction does not go.34 ‘Suggested Further Reading Price, N.C. etal. 2001) Principle and Problems in Physical Chemistry for Bochemists, ‘Ch. 8, 3rd ed, Oxford University Press, Oxford. End-of-Chapter Questions Question 4.4 In a reaction involving two reactants, A and B, the following results were obtained: (Al [B] Rate /mmol dm? _/mmol dm _/mmol dm mint 0.01 O1 2.86 x 105 0.01 02 1.14 x 104 0.02 O41 2.86 x 10° (a) What is the order with respect to each reactant? (b)_ What is the overall order? Question 4.5 Plants convert glucose to ascorbic acid (vitamin C). One step in the mechanism involves the ionisation of gluconic acid: (CyH),0,COOH = C;H,,COO- + Ht gluconie acid = gluconate anion + hydrogen ion At equilibrium it is found that the concentrations pres- ent are [CsH,,0,COOH 2.x 107 mol dm= [CsH,,0,COO7] = 6.6 x 10 mol dm [H*] = 6.6 x 10 mol dm (a) Write down the expression for the equilibrium con- stant, K,,, of this reaction, (b) Calculate the equilibrium constant. Question 4.6 In an equilibrium reaction, ASB ‘The rate constant of the forward reaction is 7.2 x 10° 7, and the rate constant of the backward reaction is 2.2 x 10 s*. Calculate the equilibrium constant for this reaction. Chemistry for Life Sciences