Professional Reference Shelf
|
|
- Christopher Reed
- 6 years ago
- Views:
Transcription
1 H. Scott Fogler Chapter 3 1/4/06 Overview Collision Theory Professional Reference Shelf A. Collision Theory In Chapter 3, we presented a number of rate laws that depended on both concentration and temperature. For the elementary reaction the elementary rate law is A + B C + D r A = kc A C B = Ae E RT C A C B We want to provide at least a qualitative understanding of why the rate law takes this form. We will first develop the collision rate, using collision theory for hard spheres of cross section S r, AB. When all collisions occur with the same relative velocity, U R, the number of collisions between A and B molecules, Z AB, is Z AB = S r U R C A C B [collisions/s/molecule] Next, we will consider a distribution of relative velocities and only consider those collisions that have an energy of E A or greater in order to react to show where r A = Ae E A RT C A C B 8k A = B T AB ) µ AB 1 N Avo with σ AB = collision radius, k B = Boltzmann s constant, µ AB = reduced mass, T = temperature, and N Avo = Avogadro s number. To obtain an estimate of E A, we use the Polyani Equation E A = E A o + P H Rx Where ΔH Rx is the heat of reaction and E o A and γ P are the Polyani Parameters. With these equations for A and E A we can make a first approximation to the rate law parameters without going to the lab. 1
2 HOT BUTTONS I. Fundamentals of Collision Theory II. Shortcomings of Collision Theory III. Modifications of Collision Theory A. Distribution of Velocities B. Collisions That Result in Reaction 1. Model 1 Pr = 0 or 1. Model Pr = 0 or Pr = E E A )/E IV. Other Definitions of Activation Energy A. Tolman s Theorem E a = E * B. Fowler and Guggenheim C. Energy Barrier V. Estimation of Activation Energy from the Polyani Equation A. Polyani Equation B. Marcus Extension of the Polyani Equation C. Blowers-Masel Relation VI. Closure References for Collision Theory, Transition State Theory, and Molecular Dynamics P. Atkins, Physical Chemistry, 6th ed. New York: Freeman, 1998) P. Atkins, Physical Chemistry, 5th ed. New York: Freeman, 1994). G. D. Billing and K. V. Mikkelsen, Introduction to Molecular Dynamics and Chemical Kinetics New York: Wiley, 1996). P.W. Atkins, The Elements of Physical Chemistry, nd ed. Oxford: Oxford Press, 1996). K. J. Laidler, Chemical Kinetics, 3rd ed. New York: Harper Collins, 1987). G. Odian, Principles of Polymerization, 3rd ed. New York: Wiley 1991). R. I. Masel, Chemical Kinetics and Catalysis New York: Wiley Interscience, 001). As a shorthand notation, we will use the following references nomenclature: A6p701 means Atkins, P. W., Physical Chemistry, 6th ed. 1998) page 701. L3p08 means Laidler, K. J., Chemical Kinetics, 3rd,ed. 1987) page 08. This nomenclature means that if you want background on the principle, topic, postulate, or equation being discussed, go to the specified page of the referenced text. I. FUNDAMENTALS OF COLLISION THEORY The objective of this development is to give the reader insight into why the rate laws depend on the concentration of the reacting species i.e., r A = kc A C B ) and why the temperature dependence is in the form of the Arrhenius law, k=ae /RT. To achieve this goal, we consider the reaction of two molecules in the gas phase A + B! C + D We will model these molecules as rigid spheres.
3 A. Rigid Spheres Species A and B are modeled as rigid spheres of radius σ A and σ B, respectively. A B! A! B Figure R3.A-1 Schematic of molecules A and B. We shall define our coordinate system such that molecule B is stationary wrt molecule A so that molecule A moves towards molecule B with a relative velocity, U R. Molecule A moves through space to sweep out a collision volume with a collision cross section,! AB, illustrated by the cylinder shown in Figure R3.A-.!AB!AB The collision radius is! AB. UR Figure R3.A- Schematic of collision cross-section.! AB =! A +! B If the center of a B molecule comes within a distance of! AB of the center of the A molecule they will collide. The collision cross section of rigid spheres is S r =! AB. As a first approximation, we shall consider S r constant. This constraint will be relaxed when we consider a distribution of relative velocities. The relative velocity between gas molecules A and B is U R. where U R = 8k BT µ AB k B = Boltzmann s constant = J/K/molecule = kg m /s /K/molecule 1 R3.A-1) This equation is given in most physical chemistry books, e.g., see Moore, W. J. Physical Chemistry, nd Ed., Englewood Cliffs, NJ: Prentice Hall, p
4 m A = mass of a molecule of species A gm) m B = mass of a molecule of species B gm) m µ AB = reduced mass = A m B g), [Let µ µ m A + m AB ] B M A = Molecular weight of A Daltons) N Avo = Avogadro s number 6.0 molecules/mol R = Ideal gas constant J/mol K = kg m /s /mol/k We note that R = N Avo k B and M A = N Avo m A, therefore we can write the ratio k B /µ AB ) as k B R = R3.A-) µ AB M A M B M A + M B An order of magnitude of the relative velocity at 300 K is U R! 3000 km hr, i.e., ten times the speed of an Indianapolis 500 Formula 1 car. The collision diameter and velocities at 0 C are given in Table R3.A-1. Molecule Table R3.A-1 Molecular Diameters Average Velocity, meters/second) Molecular Diameter Å) H CO Xe He 100. N O H O C H C 6 H CH NH H S CO N O NO Consider a molecule A moving in space. In a time Δt, the volume ΔV swept out by a molecule of A is Courtesy of J. F. O Hanlon, A User s Guide to Vacuum Technology New York: Wiley, 1980). 4
5 !l !V = U R!t ) AB!V A Figure R3.A-3 Volume swept out by molecule A in time Δt. The bends in the volume represent that even though molecule A may change directions upon collision the volume sweep out is the same. The number of collisions that will take place will be equal to the number of B molecules, ΔVC B, that are in the volume swept out by the A molecule: [ C B!V = No. of B molecules in!v] [ ] rather than [moles/dm3 ] where C B is in molecules dm 3 In a time Δt, the number of collisions of this one A molecule with many B molecules is U R C B AB t. The number of collisions of this one A molecule with all the B molecules per unit time is Z 1A B =! AB C B U R R3.A-3) However, we have many A molecules present at a concentration, C A, molecule/dm 3 ). Adding up the collisions of all the A molecules per unit volume, C A, then the number of collisions Z AB of all the A molecules with all B molecules per time per unit volume is S 67 r 8 Z AB = AB U R C A C B = S r U R C A C B R3.A-4) Where S r is the collision cross section Å). Substituting for S r and U R Z 8k AB = B T AB ) µ 1 C A C B [molecules/time/volume] R3.A-5) If we assume all collisions result in reactions, then 1 r A = Z 8k AB = B T AB * C A C B [molecules/time/volume] R3.A-6) µ ) Multiplying and dividing by Avogadrós number, N Avo, we can put our equation for the rate of reaction in terms of the number of moles/time/vol. r A N 1 Avo 3 r A 8k N Avo = )* B T AB )µ 1 C A N Avo C A C B N Avo C B N Avo R3.A-7) 5
6 1 8k r A = B T AB * N Avo µ ) 44 3 where A is the frequency factor 8k A = B T AB ) A µ AB C A C B [moles/time/volume] R3.A-8) 1 N Avo R3.A-9) r A = AC A C B R3.A-10) Example Calculate the frequency factor A for the reaction at 73K. Additional information: Using the values in Table R3.A-1 Collision Radii Hydrogen H H + O OH + O σ H =.74 Å/4 = 0.68Å = 0.68 x m Oxygen O O = 3.1 Å 1.55Å = 1.5 x m R = 8.31J mol K = kg m s K mol Solution A = S r U R N Avo R3.A-E-1) A = 8k AB U R N Avo = B T AB ) µ The relative velocity is U R = 8k B T 1 µ 1 N Avo R3.A-9) R3.A-1) Calculate the ratio k B /µ AB Let µ µ AB ) k B µ = R M A M B M A + M B = kg m s K mol 1g mol) 3g mol) 1g mol + 3g mol = 8.314kg m s K mol 0.97 g mol ) 1kg 1000g 6
7 Calculate the relative velocity k B µ = 8571m s K U R = 8 ) 73K) 8571) m s K S r = AB 3.14 Calculate the frequency factor A A = m molecule 1 = 441m s = Å s R3.A-E-) = [ A + B ] = [ m m] = m molecule [ 441m s] [ molecule mol] R3.A-E-3) A = m 3 mol s = dm 3 mol s A = m 3 mol s 1mol Å ) molecule m A = The value reported in Masel from Wesley is A = Close, but no cigar, as Groucho Marx would say. 3 R3.A-E-4) Å) 3 molecule s R3.A-E-5) Å) 3 molecule s For many simple reaction molecules, the calculated frequency factor A calc, is in good agreement with experiment. For other reactions, A calc, can be an order of magnitude too high or too low. In general, collision theory tends to overpredict the frequency factor A 10 8 dm 3 mol s < A calc <1011 dm 3 mol s Terms of cubic angstroms per molecule per second the frequency factor is 10 1 Å 3 molecule s < A calc <10 15 Å 3 molecule s There are a couple of things that are troubling about the rate of reaction given by Equation R3.A-10), i.e. M1p367. 7
8 r A = AC A C B R3.A-10) First and most obvious is the temperature dependence. A is proportional to the square root of temperature and, therefore, is r A : r A ~ A ~ T However we know that the temperature dependence of the rate of chemical reaction on temperature is given by the Arrhenius equation or r A = Ae E RT C A C B R3.A-11) E RT k = Ae R3.A-1) Next, we will discuss this shortcoming of collision theory, along with the assumption that all collisions result in reaction. II. SHORTCOMINGS OF COLLISION THEORY A. The collision theory outlined above does not account for orientation of the collision, front-to-back and along the line-of-centers. That is, molecules need to collide in the correct orientation for reaction to occur. Figure R3.A-4 shows molecules colliding whose centers are offset by a distance b. A b b = impact parameter B Figure R3.A-4 Grazing collisions. B. Collision theory does not explain activation barriers. Activation barriers occur because bonds need to be stretched or distorted in order to react and these processes require energy. Molecules must overcome electron-electron repulsion in order to come close together C. The collision theory does not explain the observed temperature dependence given by Arrhenius equation k = Ae E RT D. Collision theory assumes all A molecules have the same relative velocity, the average one. U R = 8k 1 BT R3.A-1) µ AB However, there is a distribution of velocities fu,t). One distribution most used is the Maxwell-Boltzmann distribution. Masel, 1p 8
9 III. MODIFICATIONS OF COLLISION THEORY We are now going to account for the fact that we have 1) a distribution of relative velocities U R and ) that not all collisions only those collisions with an energy E A or greater result in a reaction--the goal is to arrive at k = Ae E A RT A. Distribution of Velocities We will use the Maxwell-Boltzmann Distribution of Molecular Velocities A6p.6). For a species of mass m, the Maxwell distribution of velocities relative velocities) is f U,T)dU = 4 m k B T 3 e )mu k B T U du R3.A-13) A plot of the distribution function, fu,t), is shown as a function of U in Figure R3.A-5. T1 T!>!T1 f U,T) T Figure R3.A-5 Maxwell-Boltzmann distribution of velocities. Replacing m by the reduced mass µ of two molecules A and B f U,T)dU = 4 µ k B T 3 U e )µu k B T U du The term on the left side of Equation R3.A-13), [fu,t)du], is the fraction of molecules with velocities between U and U + du). Recall from Equation R3.A- 4) that the number of A B collisions for a reaction cross section S r is Z AB = S r U)U C 13 A k U ) C B R3.A-14) except now the collision cross-section is a function of the relative velocity. Note we have written the collision cross section S r as a function of velocity U: S r U). Why does the velocity enter into reaction cross section, S r? Because not all collisions are head on, and those that are not will not react if the energy U /µ) is not sufficiently high. Consequently, this functionality, S r = S r U), is reasonable because if two molecules collide with a very very low relative velocity it is unlikely that such a small transfer of kinetic energy is likely to activate the internal vibrations of the molecule to cause the breaking of bonds. On the other hand, for collisions with large relative velocities most collisions will result in reaction. 9
10 We now let k U) be the specific reaction rate for a collision and reaction of A-B molecules with a velocity U. [ ] R3.A-15) k U) = S r U)U m 3 molecule s Equation R3.A-15) will give the specific reaction rate and hence the reaction rate for only those collisions with velocity U. We need to sum up the collisions of all velocities. We will use the Maxwell-Boltzmann distribution for fu,t) and integrate over all relative velocities. ) = k k T U)fU,T)dU = f U,T) S r U 0 0 ) UdU R3.A-16) Maxwell distribution function of velocities for the A/B pair of reduced mass µ AB is ) = 4 f U,T Combining Equations 16) and 17) ) = S r k T µ k B T µ U 4 0 * k B T) 3 U 3 U ) µu k e B T R3.A-17) + µu k e B T du R3.A-18) For brevity, we let S r =S r U), we will now express the distribution function in terms of the translational energy ε T. We are now going to express the equation for k T) in terms of kinetic energy rather than velocity. Relating the differential translational kinetic energy, ε, to the velocity U: Multiplying and dividing by µ and hence, the reaction rate ) = 4 k T Simplifying µ k B T µ = 4 k B T! t = µu and µ, we obtain d t = µ UdU 3 ) * S 0 r µ 3 µu e + ) * S µ 0 r + t e µu 1 k B T 1, + t k B T µ µudu 1 3 d+ t dµu 1 3 d, t p185, A5p36 10
11 ) = k T 8 µ k B T ) 3 1 * + t e ) S 0 r, + t k B T d+ t [ m 3 s molecule] R3.A-19) ) = k T 8 µ k B T ) 3 1 * + S r ) t ) t e,) t k B T d) t Multiplying and dividing by k B T and noting t k B T) = E RT), we obtain ) = 8k BT k T µ 1 * ) 0 0 ) S r E +E RT Ee RT, de /. 1 R3.A-0) - RT0 Again, recall the tilde, e.g., k T), denotes that the specific reaction rate is per molecule dm 3 /molecule/s). The only thing left to do is to specify the reaction cross-section, S r E), as a function of kinetic energy E for the A/B pair of molecules. B. Collisions that Result in Reaction We now modify the hard sphere collision cross section to account for the fact that not all collisions result in reaction. Now we define S r to be the reaction cross section defined as S r = P r! AB where P r is the probability of reaction. In the first model we say the probability is either 0 or 1. In the second model P r varies from 0 to 1 continuously. We will now insert each of these modules into Equation R3.A-0). B.1 Model 1 In this model, we say only those hard collisions that have kinetic energy E A or greater will react. Let E ε t. That is, below this energy, E A, the molecules do not have sufficient energy to react so the reaction cross section is zero, S r =0. Above this kinetic energy all the molecules that collide react and the reaction crosssection is S r = AB P r = 0 P r =1 S r [ E,T] = 0 for E < E A S r [ E,T] = AB for E E A R3.A-1) R3.A-) 11
12 Figure R3.A-6 Reaction cross section for Model 1. Integrating Equation R3.A-0) by parts for the conditions given by Equations R3.A-1) and R3.A-) we obtain k = 8 k B T 1 ) 1+ E, A µ * + RT-. e/e A RT 0 AB R3.A-3) Click Back 1) ) = k T = U R AB 8 µ k B T ) E A RT ) e*e A RT Derive Click Back 1) * + T )+ T e,+ T k B T d+ T ) S o r S r = 0 < * ) = k T 8 µ k B T S r = AB ) 3 1 ) AB * +, * ** t e -* T k B T d* T 8 = AB µ k B T ) 3 ) ) 1 k B T) + *, T e -* T k B T d* T E* k B T k B T 8k = B T AB ) µ 1 * E + e,e RT de E A RT RT X = T k B T, dx = d T k B T, X = E RT, T k B T = E RT 1
13 Click Back 1 cont d) udv = uv vdu ) = AB k T 8k B T ) µ 1 * + { X e E A RT 1,X dx 3 =,Xe,X- / u dv. * / E A RT + *, e,x dx E A RT 8k = B T AB ) µ k T 1 E A 8k = B T AB ) µ + RT e *E A RT + e *E A RT. - 0, / 1 * E A E A RT > 1 ) = N Avo k T) = AB, + RT / e 0E A RT. 8k B T ) µ = A E A RT S r = P r AB 1 N Avo E A RT Over predicts the frequency factor Generally, E A >>1, so RT E A k = U R AB 1 4 RT 4 3 A e E A RT Converting k to a per mole basis rather than a per molecular basis we have 1 A = E A *8k ) B T AB N Avo RT µ 1444 AB k = A e E A RT = E A RT AeE A RT A = E A RT A We have good news and bad news. This model gives the correct temperature dependence but predicted frequency factor A is even greater than A given by Equation R3.A-9) which itself is often too large) by a factor E A /RT). So we have solved one problem, the correct temperature dependence, but created another problem, too large a frequency factor. Let s try Model. 13
14 B. Model In this model, we again assume that the colliding molecules must have an energy E A or greater to react. However, we now assume that only the kinetic energy directed along the line of centers E << is important. So below E A the reaction cross section is zero, S r =0. The kinetic energy of approach of A toward B with a velocity U R is E = µ AB U R. However, this model assumes that only ) the kinetic energy directly along the line of centers contributes to the reaction. Click Back ) Here, as E increases above E A the number of collisions that result in reaction increases. The probability for a reaction to occur is and Click Back ) P r = E E A E for E > E A R3.A-4) S r E,T) = 0 for E E A E E S r = A ) AB E for E > E A R3.A-5) R3.A-6) A U R b U LC B The impact parameter, b, is the off-set distance of the centers as they approach one another. The velocity component along the lines of centers, U LC, can be obtained by resolving the approach velocity into components. At the point of collision, the center of B is within the distance σ AB. U R b! AB Courtesy of J. I. Steinfeld, J. S. Francisco, and W. L. Hayes, Chemical Kinetics and Dynamics, Englewood Cliffs NJ: Prentice Hall, 1989, p.50); Mp
15 Click Back cont d) The energy along the line of centers can be developed by a simple geometry argument sin = b 1) AB The component of velocity along the line of centers The kinetic energy along the line of centers is U LC = U R cos θ ) E LC = U LC = U R cos = E cos 3) µ AB µ AB E LC = E[ 1 sin ] = E 1 b * 4) AB ) The minimum energy along the line of centers necessary for a reaction to take place, E A, corresponds to a critical value of the impact parameter, b crit. In fact, this is a way of defining the impact parameter and corresponding reaction cross section S r = b crit 5) Substituting for E A and b crit in Equation 4) Solving for b crit E A = E 1 b crit ) 6) b cr AB = AB 1 E A ) 7) E The reaction cross section for energies of approach, E > E A, is S r = b crit = AB The complete reaction cross section for all energies E is S r = 0 S r = AB 1 E A * 8) E ) E E A 1 E ) A + E > E A E * A plot of the reaction cross section as a function of the kinetic energy of approach E = µ AB U R 9) 10) 15
16 is shown in Figure R3.A-7. AB Model S r Model 1 Recalling Equation 0) E A E Figure R3.A-7 Reaction cross section for Models 1 and. ) = 8k B T k T Substituting for S r in Model Integrating gives Click Back 3) k T k T ) = 8k B T µ k T µ 1 1 ) = AB * ES r E)e )E RT de + R3.A-0) 0 RT ) + ) AB E * E A )e *E RT de, R3.A-7) E A RT 8k B T ) µ E E A P r = 0 S r = 0 E > E A P r =1 * ) = 8 = AB µ k B T 8 µ k B T ) 3 ) 3 ) ) 1 ) AB ) 1 e *E A RT S r = AB 1 E * A ), E +, 1* +* / e *+ kt d+ E A kt) 3 +, * e -* RT + d* - ** e **, kt ** -* kt Derive Click Back 3) d* kt 16
17 Click Back 3 cont d) k B T = E RT 8k = B T AB ) µ = k T Multiplying both sides by N Avo ) = AB Multiplying by Avogodro s number 1 E A RT + 1* E A ) e RT 8k B T ) µ k T) = Ae E A RT ) = k T k T)N Avo 1 e *E A RT *E RT Bingo! r A = AB U R N Avo e E A RT C A C B R3.A-8) This is similar to the equation for hard sphere collisions except for the term e E A RT ) = AB k T 8k B T ) µ 1 N Avo e *E A RT R3.A-9) This equation gives the correct Arrhenius dependence and the correct order of magnitude for A. r A = Ae E RT C A C B R3.A-11) Effect of Temperature on Fraction of Molecules Having Sufficient Energy to React Now we will manipulate and plot the distribution function to obtain a qualitative understanding of how temperature increases the number of reacting molecules. Figure R3.A-8 shows a plot of the distribution function given by Equation R3.A-17) after it has been converted to an energy distribution. We can write the Maxwell-Boltzmann distribution of velocities 3 µ f U,T)dU = 4 U ) µu k e B T du k B T in terms of energy by letting = µu to obtain 17
18 Derive Click back) 3 µ f U,T)dU = 4 U ) µu k e B T du k B T f t,t)d = ) 3 1 e 1 k B T k B T d t where fε,t) dε is the fraction of molecules with kinetic energies between ε and ε+dε). We could further multiply and divide by k B T. Recalling k B T = E RT f,t)de = 1 ) k B T f E,T)dE = E 1 RT f E,T) = E 1 RT 1 1 e *E RT d k B T e )E RT de RT 1 e )E RT RT f!, ) Fraction of molecules with energy! or greater!! By letting X = E, we could have put the distribution in dimensionless form RT f X,T)dX = 1 X1 e X dx fx,t) dx is the fraction of molecules that have energy ratios between E RT and E + de RT f E,T)dE = E 1 RT Fraction of collisions that have E A or above 1 e )E RT de RT Derive = * ) E A 4 RT) E 1 e +E RT de
19 This integral is shown by the shaded area on Figure R3.A-8. Figure R3.A-8 Boltzmann distribution of energies. As we just saw, only those collisions that have an energy E A or greater result in reaction. We see from Figure R3.A-10 that the higher the temperature the greater number of collision result in reaction. However, this Equations R3.A-9) and R3.A-11) cannot be used to calculate A for a number pf reactions because of steric factors and because the molecular orientation upon collision need to be considered. For example, consider a collision in which the oxygen atom, O, hits the middle carbon in the reaction to form the free radical on the middle carbon atom CH 3 C HCH 3 CH O CH 3 CH 3 C H CH 3 + OH CH Otherwise, if it hits anywhere else say the end carbon) CH 3 C H CH 3 will not be formed O CH 3 CH CH 3 CH 3 C HCH 3 CH 3 CH CH + OH Consequently, collision theory predicts a rate orders of magnitude too high for the formation of CH 3 C HCH 3. IV. OTHER DEFINITIONS OF ACTIVATION ENERGY We will only state other definitions in passing, except for the energy barrier concept, which will be discussed in transition state theory. M1p
20 ) A. Tolman s Theorem E a = E * E *! e * Average Energy of Molecules Average Energy! a = Undergoing of Colloiding + 1 Molecules kt Reaction The average transitional energy of a reactant molecule is 3 kt. B. Fowler and Guggenheim C. Energy Barrier Average Energy of Molecules Average Energy! a = Undergoing of Reactant Reaction Molecules The energy barrier concept is discussed in transition state theory, Ch3, Profession Reference Shelf B. A+ BC AB+ C A B C E E A A, BC AB, C Products Figure R3.A-9 Reaction coordinate diagram. For simple reactions, the energy, E A, can be estimated from computational chemistry programs such as Cerius or Spartan, as the heat of reaction between reactants and the transition state E A = H ABC H o o A H BC V. ESTIMATION OF ACTIVATION ENERGY FROM THE POLYANI EQUATION A. Polyani Equation The Polyani equation correlates activation energy with heat of reaction. This correlation E A = P H Rx + c R3.A-33) works well for families of reactions. For the reactions R + H R RH + R where R = OH, H, CH3, the relationship is shown in Figure R3.A-10. 0
21 Figure R3.A-10 Experimental correlation of E A and ΔH Rx. Courtesy of R. I. Masel, Chemical Kinetics and Catalysis New York: Wiley Interscience, 001). For this family of reactions E A =1 kcal mol H R For example, when the exothermic heat of reaction is The corresponding activation energy is H Rx = 10 kcal mol E a = 7cal mol R3.A-34) To develop the Polyani equation, we consider the elementary exchange reaction A+ BC AB+ C We consider the superposition of two attraction/repulsion potentials, V BC and V AB, similar to the Lennard-Jones 6-1 potential. For the molecules BC, the Lennard-Jones potential is * 1 r V BC = 4 0 LJ ) r 6 -, 0 / R3.A-35) +, r BC r BC. / where r BC = distance between molecules atoms) B and C. In addition to the Lennard-Jones 6-1 model, another model often used is the Morse potential, which has a similar shape [ ] R3.A-36) V BC = D e! r BC!r 0 )! e! r BC!r 0 ) When the molecules are far apart the potential V i.e., Energy) is zero. As they move closer together, they become attracted to one another and the potential energy reaches a minimum. As they are brought closer together, the BC molecules After R. I. Masel Loc cit). 1
22 begin to repel each other and the potential increases. Recall that the attractive force between the B and C molecules is F BC = dv BC dx R3.A-37) The attractive forces between the B C molecules are shown in Figure R3.A-11. A potential similar to atoms B and C can be drawn for the atoms A and B. The F shown in figures a and b represents the attractive force between the molecules as they move in the distances shown by the arrows. That is the attractive force increase as we move toward the well r o ) from both directions, r AB >r o and r AB <r o. BC!! AB V BC V AB kj molecule F BC! LJ F BC kj molecule F AB r 0 r BC r AB a) Figure R3.A-11 Potentials Morse or Lennard-Jones). r BC r AB r 0 b) One can also view the reaction coordinate as a variation of the BC distance for a fixed AC distance, l l l l A B C A BC AB C r AB r BC For a fixed AC distance as B moves away from C, the distance of separation of B from C, r BC increases as N moves closer to A. See point in Figure R3.A-11. As r BC increases, r AB decreases and the AB energy first decreases and then increases as the AB molecules become close. Likewise, as B moves away from A and toward C, similar energy relationships are found. E.g., as B moves toward C from A, the energy first decreases due to attraction and then increases due to repulsion of the AB molecules as they come close together at point in Figure R3.A-11. The overlapping Morse potentials are shown in Figure R3.A-11. We now superimpose the potentials for AB and BC to form Figure R3.A-1.
23 Reference BC S S 1 AB Energy E a E 1R E P!H Rx =E P E 1P r BC r 1 r* BC = r AB * r* r Reaction Coordinate r AB Figure R3.A-1 Overlap of potentials Morse or Lennard-Jones). Let S 1 be the slope of the BC line between r 1 and r BC =r AB. Starting at E 1R at r 1, the energy E 1 at a separation distance of r BC from r 1 can be calculated from the product of the slope S 1 and the distance from E 1R. The energy, E 1, of the BC molecule at any position r BC relative to r 1 is E 1 = E 1R +S 1 r BC r 1 ) R3.A-38) e.g., E 1 = 50kJ + 10kJ nm [ 5 ]nm = 0kJ ) Let S be the slope of the AB line between r and r BC =r AB. Similarly for AB, starting on the product side at E P, the energy E at any position r AB relative to r is At the height of the barrier Substituting for E 1 and E E = E P +S r AB r ) R3.A-39) * e.g., E = 80kJ + 0kJ -, ) 7 10)nm = 0kJ/ + nm. E 1 = E at r BC = r AB R3.A-40) Rearranging E 1R +S 1 r BC r 1 S 1 r BC r 1 ) = E P +S r AB ) = E P E 1R ) +S r AB r H Rx r ) R3.A-41) ) R3.A-4) 3
24 yields r BC = r AB = r S 1 r r 1 ) = H Rx +S r r ) Solving for r* and substituting back into the Equation E a = E 1 E 1R = S 1 r r 1 E a = E a! + P H Rx ) R3.A-43) Derive click back) see p.19) R3.A-44) Equation 8) gives the Polyani correlation relating activation energy and heat of reaction. Values of E a o and γ P for different reactions can be found in Table 5.4 on page 54 of Masel. One of the more common correlations for exothermic and endothermic reactions is given on page 73 of Laidler. 1) Exothermic Reactions E a = H Rx If H Rx = 100kJ mol, then E a = ) 100 kj mol ) E a = 3.1kJ mol ) kj mol R3.A-45) ) Endothermic Reactions E a = H Rx ) kj mol R3.A-46) E a = ) 100 kj mol) =19 kj mol = 9 kcal mol Also see R. Masel Chemical Kinetics and catalysis, p603 to calculate the activation energy from the heat of reaction. Szabo proposed an extension of Polyani equation E a = D j Breaking) D j Forming) R3.A-47) D i = Dissociation Energies Derive Click back) S 1 r r 1 ) = H Rx +S r r ) A) Rearranging S 1 S )r = H Rx +S 1 r 1 S r B) Solving for r* r = H Rx ) + S 1 r 1 S r S 1 S S 1 S C) 4
25 Recalling Equation R3.A-43) E a = E 1 E 1R = S 1 r r 1 ) R3.A-43) Substituting Equation C) for r* in Equation R3.A-43) Rearranging H E a = S Rx 1 + S 1r 1 S r )S 1 r 1 E) S 1 S S 1 S S E a = 1 * S )H Rx +S 1 r 1 S r - 1, r 1 / F) S 1 S + S 1 S. S = 1 * S )H Rx +S 1 r 1 S r S 1 r 1 +S r 1-1, / G) S 1 S + S 1 S. Finally, collecting terms we have S E a = 1 *H Rx + S 1S [ r 1 r ] S S S S ) P Note: S 1 is positive, S is negative, and r > r 1 ; therefore, E a! is positive, as is γ P. E a = E a! + p H Rx E a + H) B. Marcus Extension of the Polyani Equation In reasoning similar to developing the Polyani Equation, Marcus shows see Masel, pp ) E A = 1+ H Rx 4E A0 E A0 C. Blowers-Masel Relation The Polyani Equation will predict negative activation energies for highly exothermic reactions. Blowers and Masel developed a relationship that compares quite well with experiments throughout the entire range of heat of reaction for the family of reactions as shown in Figure R3.A-13. R + H R RH + R 5
26 VI. CLOSURE Figure R3.A-13 Comparison of models with data. Courtesy of R. I. Masel, Chemical Kinetics and Catalysis New York: Wiley Interscience, 001). We see the greatest agreement between theory and experiment is found with the Blowers-Masel model. We have now developed a quantitative and qualitative understanding of the concentration and temperature dependence of the rate law for reactions such as with A + B C + D r A = k C A C B We have also developed first estimates for the frequency factor, A, from collision theory 1 8k A = S r U R N Avo = B T AB ) N Avo µ AB and the activation energy, E A, from the Polyani Equation. E A = E A o + P H Rx These calculated values for A and EA can be substituted in the rate law to determine rates of reaction. r A = kc A C B = Ae E A RT 6
27 VI. OTHER STUFF Potential Energy Surfaces and the barrier height ε hb Figure R3.A-14 Reaction coordinates. The average transitional energy of a molecule undergoing collision is k B T. The molecules with a higher energy are more likely to collide. A. How to Calculate Barrier Height 1) Ab Initio calculations. No adjustment of parameters or use of experimental data. Solve Schrödinger s Equation E b = Barrier Height ε hb E b = 40 kj/mol for the H + H exchange reaction ) Semiempirical Uses experimental measurements spectroscopic). Adjustments are made to get agreement. 3) London-Eyring-Polanyi LEP) Method LEP) Surface Use spectroscopic measurement in conjunction with the Morse potential equation E = D e! r!r 0 )! e! r!r 0 ) [ ] D = dissociation energy r o = equilibrium internuclear distance β = constant Model B3 Stored Energy This third method considers vibrational and translation energy in addition to translational energy. Even though this approach is oversimplified, it is satisfying because it gives a qualitative feel for the Arrhenius temperature dependence. In this approach, we say the fraction of molecules that will react are those that have acquired an energy E A. 7
28 Maxwell-Boltzmann Statistics for n Degrees of Freedom Here, energy can be stored in the molecule by different modes. For n degrees of freedom transitional, vibrational, and rotational) L3p76) kt f,t) = 1 n 1 ) e R3.A-30) k )! B T k B T df = f,t)d = fraction of molecules with energy between ε and ε + dε) For methane, there are 3 transitional, 3 rotational, and 9 vibrational degrees of freedom, n = 15. Because Equation 31) is awkward, the two dimension equation is often used, with n = and the distribution function is n f,t) = e k B T k B T R3.A-31) Activation Energy From the Maxwell-Boltzmann distribution of velocities we obtain the distribution of energies of the molecules as shown below. Here, fdε is the fraction, df, of molecules between ε and ε + dε. df = f,t)d We now say only those molecules that have an energy, E A or greater, will react. Integrating between the limits E* i.e., E A ) and infinity, we find the fraction of molecules colliding with energy E A or greater F = 1 k B T d e k BT * Multiplying and dividing by k B T and noting again Integrating df = e E RT de E A F = e E A RT k B T = E RT R3.A-3) We now say that this is the fraction of collisions that have energy, E A or greater, and can react. Multiplying this fraction times the number of collisions, e.g., Equation R3.A-10), gives r A = Ae E A RT C A C B which gives the Arrhenius Equation k = A e E A RT * kt = A e 8
3. RATE LAW AND STOICHIOMETRY
Page 1 of 39 3. RATE LAW AND STOICHIOMETRY Professional Reference Shelf R3.2 Abbreviated Lecture Notes Full Lecture Notes I. Overview II. Introduction A. The Transition State B. Procedure to Calculate
More informationCFC: chlorofluorocarbons
The rate of reaction is markedly affected by temperature. Chemical Kinetics & k versus T Two theories were developed to explain the temperature effects. 1. 2. 2 UV radiation strikes a CFC molecule causing
More informationCHEM Chemical Kinetics. & Transition State Theory
Chemical Kinetics Collision Theory Collision Theory & Transition State Theory The rate of reaction is markedly affected by temperature. k versus T Ae E a k RT Two theories were developed to explain the
More information2013, 2011, 2009, 2008 AP
Lecture 15 Thermodynamics I Heat vs. Temperature Enthalpy and Work Endothermic and Exothermic Reactions Average Bond Enthalpy Thermodynamics The relationship between chemical reactions and heat. What causes
More informationCHAPTER 9 LECTURE NOTES
CHAPTER 9 LECTURE NOTES 9.1, 9.2: Rate of a reaction For a general reaction of the type A + 3B 2Y, the rates of consumption of A and B, and the rate of formation of Y are defined as follows: Rate of consumption
More informationAssignment: Read Atkins, Chapter 27 sections 7 and 8 or McQuarrie and Simon, Chapter 30 sections 7 and 10, before coming to lab on Monday
Classical Trajectory 1 Classical Trajectory Calculations H + H-F H-H + F Assignment: Read Atkins, Chapter 27 sections 7 and 8 or McQuarrie and Simon, Chapter 30 sections 7 and 10, before coming to lab
More informationRates and Temperature
Rates and Temperature N Goalby Chemrevise.org Activation Energy Molecules will only react if they collide with enough energy to break the relevant bonds in one or either of the reactant molecules. This
More informationIdeal Gas Behavior. NC State University
Chemistry 331 Lecture 6 Ideal Gas Behavior NC State University Macroscopic variables P, T Pressure is a force per unit area (P= F/A) The force arises from the change in momentum as particles hit an object
More informationIn order for two molecules to react, they must with each other. When they collide they transfer among themselves.
Chemistry 12 Reaction Kinetics II Name: Date: Block: 1. Collision Theory 2. Activation Energy 3. Potential Energy Diagrams Collision Theory (Kinetic Molecular Theory) In order for two molecules to react,
More informationPHEN 612 SPRING 2008 WEEK 1 LAURENT SIMON
PHEN 612 SPRING 2008 WEEK 1 LAURENT SIMON Chapter 1 * 1.1 Rate of reactions r A A+B->C Species A, B, and C We are interested in the rate of disappearance of A The rate of reaction, ra, is the number of
More information(Ox) 6I - (aq) + BrO 3 - (aq) + 6H + (aq) 3I 2 (aq) + Br - (aq) + 3H 2 O(l)
Creating an Energy Profile For the Aqueous xidation of odide by omate in Acid The net ionic equation for the process we are investigating (x) is depicted below. (x) 6 - (aq) + - (aq) + 6 + (aq) 2 (aq)
More informationReview of Fitting Kinetic Data
L6-1 Review of Fitting Kinetic Data True or false: The goal of fitting kinetic data is to find the true rate expression. What are the two general methods used to fit kinetic data? L6-2 Advantages and Drawbacks
More informationwith increased Lecture Summary #33 Wednesday, December 3, 2014
5. Lecture Summary #33 Wednesday, December 3, 204 Reading for Today: 4.-4.3 in 5 th ed and 3.-3.3 in 4 th ed Reading for Lecture #34: 4.4 & 4.6 in 5 th ed and 3.4 & 3.6 in 4 th ed Topic: Kinetics I. Effect
More informationTransition Theory Abbreviated Derivation [ A - B - C] # E o. Reaction Coordinate. [ ] # æ Æ
Transition Theory Abbreviated Derivation A + BC æ Æ AB + C [ A - B - C] # E A BC D E o AB, C Reaction Coordinate A + BC æ æ Æ æ A - B - C [ ] # æ Æ æ A - B + C The rate of reaction is the frequency of
More informationBrown, LeMay Ch 5 AP Chemistry Monta Vista High School
Brown, LeMay Ch 5 AP Chemistry Monta Vista High School 1 From Greek therme (heat); study of energy changes in chemical reactions Energy: capacity do work or transfer heat Joules (J), kilo joules (kj) or
More information4 th Edition Chapter 9
Insert Page 547A 4 th Edition Chapter 9 In summary, if any one of the following three things had not occurred the explosion would not have happened. 1. Tripled production 2. Heat exchanger failure for
More informationProfessional Reference Shelf
hapter 3 H. Scott Fogler /4/5 Professional Reference Shelf. Molecular Dynamics Overview H + H æ Æ H + H + æ Æ + (1) alculate potential energy surface, V ( R,R,R ) () arry of Trajectory alculations The
More informationCh 6. Energy and Chemical Change. Brady & Senese, 5th Ed.
Ch 6. Energy and Chemical Change Brady & Senese, 5th Ed. Energy Is The Ability To Do Work Energy is the ability to do work (move mass over a distance) or transfer heat Types: kinetic and potential kinetic:
More information2 Reaction kinetics in gases
2 Reaction kinetics in gases October 8, 2014 In a reaction between two species, for example a fuel and an oxidizer, bonds are broken up and new are established in the collision between the species. In
More informationis the Michaelis constant. It represents the apparent dissociation constant of ES to E and S.
Lecture 35 Chapt 28, Sections 1-4 Bimolecular reactions in the gas phase Anouncements: Exam tomorrow 2:00 is the primary time. vdw 237 I have gotten several suggestions for lecture ideas, thanks and keep
More informationChapter 13 - Chemical Kinetics II. Integrated Rate Laws Reaction Rates and Temperature
Chapter 13 - Chemical Kinetics II Integrated Rate Laws Reaction Rates and Temperature Reaction Order - Graphical Picture A ->Products Integrated Rate Laws Zero Order Reactions Rate = k[a] 0 = k (constant
More informationChem 116 POGIL Worksheet - Week 6 Kinetics - Concluded
Chem 116 POGIL Worksheet - Week 6 Kinetics - Concluded Why? The half-life idea is most useful in conjunction with first-order kinetics, which include many chemical reactions and all nuclear decay processes.
More informationThermochemistry. Energy. 1st Law of Thermodynamics. Enthalpy / Calorimetry. Enthalpy of Formation
THERMOCHEMISTRY Thermochemistry Energy 1st Law of Thermodynamics Enthalpy / Calorimetry Hess' Law Enthalpy of Formation The Nature of Energy Kinetic Energy and Potential Energy Kinetic energy is the energy
More informationconcentrations (molarity) rate constant, (k), depends on size, speed, kind of molecule, temperature, etc.
#73 Notes Unit 9: Kinetics and Equilibrium Ch. Kinetics and Equilibriums I. Reaction Rates NO 2(g) + CO (g) NO (g) + CO 2(g) Rate is defined in terms of the rate of disappearance of one of the reactants,
More informationChemical Kinetics and Equilibrium
Chemical Kinetics and Equilibrium Part 1: Kinetics David A. Katz Department of Chemistry Pima Community College Tucson, AZ USA Chemical Kinetics The study of the rates of chemical reactions and how they
More informationEnergy Barriers and Rates - Transition State Theory for Physicists
Energy Barriers and Rates - Transition State Theory for Physicists Daniel C. Elton October 12, 2013 Useful relations 1 cal = 4.184 J 1 kcal mole 1 = 0.0434 ev per particle 1 kj mole 1 = 0.0104 ev per particle
More informationGeneral Chemistry I Concepts
Chemical Kinetics Chemical Kinetics The Rate of a Reaction (14.1) The Rate Law (14.2) Relation Between Reactant Concentration and Time (14.3) Activation Energy and Temperature Dependence of Rate Constants
More informationChapter 11 Rate of Reaction
William L Masterton Cecile N. Hurley http://academic.cengage.com/chemistry/masterton Chapter 11 Rate of Reaction Edward J. Neth University of Connecticut Outline 1. Meaning of reaction rate 2. Reaction
More informationC H E M I C N E S C I
C H E M I C A L K I N E T S C I 4. Chemical Kinetics Introduction Average and instantaneous Rate of a reaction Express the rate of a reaction in terms of change in concentration Elementary and Complex
More information10 Reaction rates and equilibrium Answers to practice questions. OCR Chemistry A. number 1 (a) 1: The enthalpy change, H;
1 (a) 1: The enthalpy change, H; 2: The activation energy, E a 1 (b) H is unaffected as it is the difference between the reactants and products E a decreases as a catalyst allows an alternative route of
More informationCY T. Pradeep. Lectures 11 Theories of Reaction Rates
CY1001 2015 T. Pradeep Lectures 11 Theories of Reaction Rates There are two basic theories: Collision theory and activated complex theory (transition state theory). Simplest is the collision theory accounts
More informationPhysics 160 Thermodynamics and Statistical Physics: Lecture 2. Dr. Rengachary Parthasarathy Jan 28, 2013
Physics 160 Thermodynamics and Statistical Physics: Lecture 2 Dr. Rengachary Parthasarathy Jan 28, 2013 Chapter 1: Energy in Thermal Physics Due Date Section 1.1 1.1 2/3 Section 1.2: 1.12, 1.14, 1.16,
More informationCHEMICAL KINETICS (RATES OF REACTION)
Kinetics F322 1 CHEMICAL KINETICS (RATES OF REACTION) Introduction Chemical kinetics is concerned with the dynamics of chemical reactions such as the way reactions take place and the rate (speed) of the
More informationElementary Reactions
Elementary Reactions Elementary reactions occur in a single encounter Unimolecular: A Rate = k[a] Bimolecular: A + B Rate = k[a][b] Termolecular: A + B + C Rate = k[a][b][c] Termolecular reactions are
More informationChapter 6 Energy and Chemical Change. Brady and Senese 5th Edition
Chapter 6 Energy and Chemical Change Brady and Senese 5th Edition Index 6.1 An object has energy if it is capable of doing work 6.2 Internal energy is the total energy of an object s molecules 6.3 Heat
More informationUnit 13: Rates and Equilibrium- Guided Notes
Name: Period: What is a Chemical Reaction and how do they occur? Unit 13: Rates and Equilibrium- Guided Notes A chemical reaction is a process that involves of atoms Law of Conservation of : Mass is neither
More informationIdeal Gas Law. Deduced from Combination of Gas Relationships: PV = nrt. where R = universal gas constant
Ideal Gas Law Deduced from Combination of Gas Relationships: V 1/P, Boyle's Law V T, Charles's Law V n, Avogadro's Law Therefore, V nt/p or PV nt PV = nrt where R = universal gas constant The empirical
More informationRates of Chemical Reactions
Rates of Chemical Reactions Jim Birk 12-1 Questions for Consideration 1. What conditions affect reaction rates? 2. How do molecular collisions explain chemical reactions? 3. How do concentration, temperature,
More informationREACTION KINETICS. Catalysts substances that increase the rates of chemical reactions without being used up. e.g. enzymes.
REACTION KINETICS Study of reaction rates Why? Rates of chemical reactions are primarily controlled by 5 factors: the chemical nature of the reactants 2 the ability of the reactants to come in contact
More information12A Entropy. Entropy change ( S) N Goalby chemrevise.org 1. System and Surroundings
12A Entropy Entropy change ( S) A SPONTANEOUS PROCESS (e.g. diffusion) will proceed on its own without any external influence. A problem with H A reaction that is exothermic will result in products that
More informationENTHALPY CHANGE CHAPTER 4
ENTHALPY CHANGE CHAPTER 4 ENTHALPY Is the total energy of a system. E k = Kinetic energy. Vibrational Rotational Translational E due to motion H = E k + E p E P = Potential energy Attractive force b/w
More informationThe Study of Chemical Reactions. Mechanism: The complete, step by step description of exactly which bonds are broken, formed, and in which order.
The Study of Chemical Reactions Mechanism: The complete, step by step description of exactly which bonds are broken, formed, and in which order. Thermodynamics: The study of the energy changes that accompany
More informationΔx Δt. Any average rate can be determined between measurements at 2 points in time.
Chapter 13 Chemical Kinetics Some reaction are faster than others! Chem 210 Jasperse Ch. 13 Handouts 1 Three factors (in addition to the nature of the reacting chemicals themselves ) 1. Concentrations
More informationHEAT, TEMPERATURE, & THERMAL ENERGY. Work - is done when an object is moved through a distance by a force acting on the object.
HEAT, TEMPERATURE, & THERMAL ENERGY Energy A property of matter describing the ability to do work. Work - is done when an object is moved through a distance by a force acting on the object. Kinetic Energy
More informationExpress the transition state equilibrium constant in terms of the partition functions of the transition state and the
Module 7 : Theories of Reaction Rates Lecture 33 : Transition State Theory Objectives After studying this Lecture you will be able to do the following. Distinguish between collision theory and transition
More informationLaboratory Measurement Values and Kinetic Theory
Laboratory Measurement alues and Kinetic Theory Kinetic Theory is an attempt to explain macroscopic phenomena such as pressure, reaction rates diffusion rates, etc by using basic principles of motion.
More informationFactors That Affect Rates. Factors That Affect Rates. Factors That Affect Rates. Factors That Affect Rates
KINETICS Kinetics Study of the speed or rate of a reaction under various conditions Thermodynamically favorable reactions DO NOT mean fast reactions Some reactions take fraction of a second (explosion)
More informationThe Nature of Energy. Chapter Six: Kinetic vs. Potential Energy. Energy and Work. Temperature vs. Heat
The Nature of Energy Chapter Six: THERMOCHEMISTRY Thermodynamics is the study of energy and its transformations. Thermochemistry is the study of the relationship between chemical reactions and energy changes
More informationAP Chemistry - Notes - Chapter 12 - Kinetics Page 1 of 7 Chapter 12 outline : Chemical kinetics
AP Chemistry - Notes - Chapter 12 - Kinetics Page 1 of 7 Chapter 12 outline : Chemical kinetics A. Chemical Kinetics - chemistry of reaction rates 1. Reaction Rates a. Reaction rate- the change in concentration
More informationAdiabatic Expansion/Compression
Adiabatic Expansion/Compression Calculate the cooling in a the reversible adiabatic expansion of an ideal gas. P P 1, 1, T 1 A du q w First Law: Since the process is adiabatic, q = 0. Also w = -p ex d
More informationUnit I: Reaction Kinetics Introduction:
Chemistry 12 Unit I: Reaction Kinetics Introduction: Kinetics Definition: All reactions occur at different rates Examples: Slow Reactions Fast Reactions Chemists need to understand kinetics because sometimes
More informationALE 4. Effect of Temperature and Catalysts on the Rate of a Chemical Reaction
Name Chem 163 Section: Team Number: ALE 4. Effect of Temperature and Catalysts on the Rate of a Chemical Reaction (Reference: 16.5 16.6 & 16.8 Silberberg 5 th edition) Why do reaction rates increase as
More informationQuickCheck. Collisions between molecules. Collisions between molecules
Collisions between molecules We model molecules as rigid spheres of radius r as shown at the right. The mean free path of a molecule is the average distance it travels between collisions. The average time
More information5.2 Energy. N Goalby chemrevise.org Lattice Enthalpy. Definitions of enthalpy changes
5.2 Energy 5.2.1 Lattice Enthalpy Definitions of enthalpy changes Enthalpy change of formation The standard enthalpy change of formation of a compound is the energy transferred when 1 mole of the compound
More informationCollisions between molecules
Collisions between molecules We model molecules as rigid spheres of radius r as shown at the right. The mean free path of a molecule is the average distance it travels between collisions. The average time
More informationPotential Barriers and Tunneling
Potential Barriers and Tunneling Mark Ellison Department of Chemistry Wittenberg University Springfield, OH 45501 mellison@wittenberg.edu Copyright 004 by the Division of Chemical Education, Inc., American
More information1.3 Molecular Level Presentation
1.3.1 Introduction A molecule is the smallest chemical unit of a substance that is capable of stable, independent existence. Not all substances are composed of molecules. Some substances are composed of
More informationReaction Mechanisms Dependence of rate on temperature Activation Energy E a Activated Complex Arrhenius Equation
Kinetics Dependence of rate on Concentration (RATE LAW) Reaction Mechanisms Dependence of rate on temperature Activation Energy E a Activated Complex Arrhenius Equation Mary J. Bojan Chem 112 1 A MECHANISM
More informationOutline: Kinetics. Reaction Rates. Rate Laws. Integrated Rate Laws. Half-life. Arrhenius Equation How rate constant changes with T.
Chemical Kinetics Kinetics Studies the rate at which a chemical process occurs. Besides information about the speed at which reactions occur, kinetics also sheds light on the reaction mechanism (exactly
More informationChapter 14. Chemical Kinetics
Chapter 14. Chemical Kinetics Common Student Misconceptions It is possible for mathematics to get in the way of some students understanding of the chemistry of this chapter. Students often assume that
More informationBrown et al, Chemistry, 2nd ed (AUS), Ch. 12:
Kinetics: Contents Brown et al, Chemistry, 2 nd ed (AUS), Ch. 12: Why kinetics? What is kinetics? Factors that Affect Reaction Rates Reaction Rates Concentration and Reaction Rate The Change of Concentration
More informationCHEMICAL KINETICS. Collision theory and concepts, activation energy and its importance VERY SHORT ANSWER QUESTIONS
Topic-3 CHEMICAL KINETICS Collision theory and concepts, activation energy and its importance 1. What is law of mass action? VERY SHORT ANSWER QUESTIONS This law relates rate of reaction with active mass
More information1.8 Thermodynamics. N Goalby chemrevise.org. Definitions of enthalpy changes
1.8 Thermodynamics Definitions of enthalpy changes Enthalpy change of formation The standard enthalpy change of formation of a compound is the energy transferred when 1 mole of the compound is formed from
More information11/2/ and the not so familiar. Chemical kinetics is the study of how fast reactions take place.
Familiar Kinetics...and the not so familiar Reaction Rates Chemical kinetics is the study of how fast reactions take place. Some happen almost instantaneously, while others can take millions of years.
More informationEnergy in Chemical Reaction Reaction Rates Chemical Equilibrium. Chapter Outline. Energy 6/29/2013
Energy in Chemical Reaction Reaction Rates Chemical Equilibrium Chapter Outline Energy change in chemical reactions Bond dissociation energy Reaction rate Chemical equilibrium, Le Châtelier s principle
More informationChapter Seven. Chemical Reactions: Energy, Rates, and Equilibrium
Chapter Seven Chemical Reactions: Energy, Rates, and Equilibrium Endothermic vs. Exothermic 2 Endothermic: A process or reaction that absorbs heat and has a positive ΔH. Exothermic: A process or reaction
More informationTHERMODYNAMICS. Topic: 5 Gibbs free energy, concept, applications to spontaneous and non-spontaneous processes VERY SHORT ANSWER QUESTIONS
THERMODYNAMICS Topic: 5 Gibbs free energy, concept, applications to spontaneous and non-spontaneous processes 1. What is Gibbs energy? VERY SHORT ANSWER QUESTIONS Gibbs energy (G): The amount of energy
More informationHandout 11: Ideal gas, internal energy, work and heat. Ideal gas law
Handout : Ideal gas, internal energy, work and heat Ideal gas law For a gas at pressure p, volume V and absolute temperature T, ideal gas law states that pv = nrt, where n is the number of moles and R
More informationChE 344 Winter 2013 Final Exam + Solution. Open Course Textbook Only Closed everything else (i.e., Notes, In-Class Problems and Home Problems
ChE 344 Winter 03 Final Exam + Solution Thursday, May, 03 Open Course Textbook Only Closed everything else (i.e., Notes, In-Class Problems and Home Problems Name Honor Code (Please sign in the space provided
More informationChapter 6 Chemical Reactivity and Mechanisms
Chapter 6 Chemical Reactivity and Mechanisms 6.1 Enthalpy Enthalpy (ΔH or q) is the heat energy exchange between the reaction and its surroundings at constant pressure Breaking a bond requires the system
More informationconcentrations (molarity) rate constant, (k), depends on size, speed, kind of molecule, temperature, etc.
#80 Notes Ch. 12, 13, 16, 17 Rates, Equilibriums, Energies Ch. 12 I. Reaction Rates NO 2(g) + CO (g) NO (g) + CO 2(g) Rate is defined in terms of the rate of disappearance of one of the reactants, but
More informationEnergy Changes, Reaction Rates and Equilibrium. Thermodynamics: study of energy, work and heat. Kinetic energy: energy of motion
Energy Changes, Reaction Rates and Equilibrium Thermodynamics: study of energy, work and heat Kinetic energy: energy of motion Potential energy: energy of position, stored energy Chemical reactions involve
More informationCh 13 Rates of Reaction (Chemical Kinetics)
Ch 13 Rates of Reaction (Chemical Kinetics) Reaction Rates and Kinetics - The reaction rate is how fast reactants are converted to products. - Chemical kinetics is the study of reaction rates. Kinetics
More informationAdsorption of gases on solids (focus on physisorption)
Adsorption of gases on solids (focus on physisorption) Adsorption Solid surfaces show strong affinity towards gas molecules that it comes in contact with and some amt of them are trapped on the surface
More information2/23/2018. Familiar Kinetics. ...and the not so familiar. Chemical kinetics is the study of how fast reactions take place.
CHEMICAL KINETICS & REACTION MECHANISMS Readings, Examples & Problems Petrucci, et al., th ed. Chapter 20 Petrucci, et al., 0 th ed. Chapter 4 Familiar Kinetics...and the not so familiar Reaction Rates
More information1. A. Define the term rate of reaction. The measure of the amount of reactants being converted into products per unit amount of time
Name answer key period IB topic 6 Kinetics 1. A. Define the term rate of reaction. The measure of the amount of reactants being converted into products per unit amount of time b. the reaction between C
More informationPhysics Dec The Maxwell Velocity Distribution
Physics 301 7-Dec-2005 29-1 The Maxwell Velocity Distribution The beginning of chapter 14 covers some things we ve already discussed. Way back in lecture 6, we calculated the pressure for an ideal gas
More information5.1 Exothermic and endothermic reactions
Topic 5: Energetics 5.1 Exothermic and endothermic reactions Chemical reactions involve the breaking and making of bonds. Breaking bonds requires energy,whereas energy is given out when new bonds are formed.
More information7/19/2011. Models of Solution. State of Equilibrium. State of Equilibrium Chemical Reaction
Models of Solution Chemistry- I State of Equilibrium A covered cup of coffee will not be colder than or warmer than the room temperature Heat is defined as a form of energy that flows from a high temperature
More informationELEMENTARY CHEMICAL KINETICS
ELEMENTARY CHEMICAL KINETICS EDR Chapter 25... a knowledge of the rate, or time dependence, of chemical change is of critical importance for the successful synthesis of new materials and for the utilization
More informationCHAPTER 21: Reaction Dynamics
CHAPTER 21: Reaction Dynamics I. Microscopic Theories of the Rate Constant. A. The Reaction Profile (Potential Energy diagram): Highly schematic and generalized. A---B-C B. Collision Theory of Bimolecular
More informationThermochemistry: Heat and Chemical Change
Thermochemistry: Heat and Chemical Change 1 Heat or Thermal Energy (q) Heat is a form of energy Is heat the same as temperature? Heat flows between two objects at different temperatures. Hot Cold 2 Chemical
More informationChapter 13 Kinetics: Rates and Mechanisms of Chemical Reactions
Chapter 13 Kinetics: Rates and Mechanisms of Chemical Reactions 14.1 Focusing on Reaction Rate 14.2 Expressing the Reaction Rate 14.3 The Rate Law and Its Components 14.4 Integrated Rate Laws: Concentration
More informationCHAPTER 13 (MOORE) CHEMICAL KINETICS: RATES AND MECHANISMS OF CHEMICAL REACTIONS
CHAPTER 13 (MOORE) CHEMICAL KINETICS: RATES AND MECHANISMS OF CHEMICAL REACTIONS This chapter deals with reaction rates, or how fast chemical reactions occur. Reaction rates vary greatly some are very
More informationA Study of the Thermal Properties of a One. Dimensional Lennard-Jones System
A Study of the Thermal Properties of a One Dimensional Lennard-Jones System Abstract In this study, the behavior of a one dimensional (1D) Lennard-Jones (LJ) system is simulated. As part of this research,
More information1.4 Enthalpy. What is chemical energy?
1.4 Enthalpy What is chemical energy? Chemical energy is a form of potential energy which is stored in chemical bonds. Chemical bonds are the attractive forces that bind atoms together. As a reaction takes
More informationOutline of the Course
Outline of the Course 1) Review and Definitions 2) Molecules and their Energies 3) 1 st Law of Thermodynamics 4) 2 nd Law of Thermodynamics 5) Gibbs Free Energy 6) Phase Diagrams and REAL Phenomena 7)
More informationENZYME SCIENCE AND ENGINEERING PROF. SUBHASH CHAND DEPARTMENT OF BIOCHEMICAL ENGINEERING AND BIOTECHNOLOGY IIT DELHI LECTURE 3
ENZYME SCIENCE AND ENGINEERING PROF. SUBHASH CHAND DEPARTMENT OF BIOCHEMICAL ENGINEERING AND BIOTECHNOLOGY IIT DELHI LECTURE 3 ENZYMES AS BIOCATALYSTS * CATALYTIC EFFICIENCY *SPECIFICITY Having discussed
More informationChapter 14. Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten Chapter 14 John D. Bookstaver St. Charles Community College St. Peters, MO 2006, Prentice Hall,
More informationGases: Their Properties & Behavior. Chapter 09 Slide 1
9 Gases: Their Properties & Behavior Chapter 09 Slide 1 Gas Pressure 01 Chapter 09 Slide 2 Gas Pressure 02 Units of pressure: atmosphere (atm) Pa (N/m 2, 101,325 Pa = 1 atm) Torr (760 Torr = 1 atm) bar
More information3.2 Calorimetry and Enthalpy
3.2 Calorimetry and Enthalpy Heat Capacity Specific heat capacity (c) is the quantity of thermal energy required to raise the temperature of 1 g of a substance by 1 C. The SI units for specific heat capacity
More informationChemistry 1A, Spring 2007 Midterm Exam 3 April 9, 2007 (90 min, closed book)
Chemistry 1A, Spring 2007 Midterm Exam 3 April 9, 2007 (90 min, closed book) Name: KEY SID: TA Name: 1.) Write your name on every page of this exam. 2.) This exam has 34 multiple choice questions. Fill
More informationThe following gas laws describes an ideal gas, where
Alief ISD Chemistry STAAR Review Reporting Category 4: Gases and Thermochemistry C.9.A Describe and calculate the relations between volume, pressure, number of moles, and temperature for an ideal gas as
More informationEnergy, Heat and Chemical Change
Energy, Heat and Chemical Change Chemistry 35 Fall 2000 Thermochemistry A part of Thermodynamics dealing with energy changes associated with physical and chemical reactions Why do we care? -will a reaction
More informationChapter 12. Chemical Kinetics
Chapter 12 Chemical Kinetics Section 12.1 Reaction Rates Section 12.1 Reaction Rates Section 12.1 Reaction Rates Section 12.1 Reaction Rates Section 12.1 Reaction Rates Section 12.1 Reaction Rates Section
More informationLecture 22: The Arrhenius Equation and reaction mechanisms. As we wrap up kinetics we will:
As we wrap up kinetics we will: Lecture 22: The Arrhenius Equation and reaction mechanisms. Briefly summarize the differential and integrated rate law equations for 0, 1 and 2 order reaction Learn how
More informationGases. Properties of Gases Kinetic Molecular Theory of Gases Pressure Boyle s and Charles Law The Ideal Gas Law Gas reactions Partial pressures.
Gases Properties of Gases Kinetic Molecular Theory of Gases Pressure Boyle s and Charles Law The Ideal Gas Law Gas reactions Partial pressures Gases Properties of Gases All elements will form a gas at
More informationChem 401 Unit 1 (Kinetics & Thermo) Review
KINETICS 1. For the equation 2 H 2(g) + O 2(g) 2 H 2 O (g) How is the rate of formation of H 2 O mathematically related to the rate of disappearance of O 2? 1 Δ [H2O] Δ[O 2] = 2 Δt Δt 2. Determine the
More informationFACTFILE: GCE CHEMISTRY
FACTFILE: GCE CHEMISTRY 2.9 KINETICS Learning Outcomes Students should be able to: 2.9.1 recall how factors, including concentration, pressure, temperature and catalyst, affect the rate of a chemical reaction;
More informationCHAPTER III: Kinetic Theory of Gases [5%]
CHAPTER III: Kinetic Theory of Gases [5%] Introduction The kinetic theory of gases (also known as kinetic-molecular theory) is a law that explains the behavior of a hypothetical ideal gas. According to
More information