( Chapter 8 ) \ / Differential Calculus with Several Independent Variables Principal Facts and Ideas + Functions of several independent variables occur fre quently in physical chemistry, both in thermodynamics and in quantum mechanics. # A derivative of a function of several variables with respect fo one independent variable is called a partial derivative, The other variables are treated as constants during the differentiation, + There are some useful identities that allow manipula tions of expressions containing partial derivatives # The differential of a function of several variables (an exact differential) has one term for each variable, consisting of a partial derivative times the differential of the independent variable. This differential form delivers the value of an infinitesimal change in the function produced by infinitesimal changes in the independent variables, «Differential forms exist that are not the differentials of any function. Such a differential form is called an inexact differential, « Relative maxima and minima of a function of several variables are found by solving simultaneously the equations obtained by setting all partial derivatives equal to zero. © Constrained maxima and minima of a function of several variables can be found by the method of Lagrange multipliers. + The gradient operator isa vector derivative operator that produces a vector when applied to a scalar function, + The divergence operator is a vector derivative operator that produces a scalar when applied to vector function, + The curl operator is a vector derivative operator that produces a veetor when applied to a veetor function Maem fe Phnom ptr0 OBI.258.210082 ‘* The Laplacian operator is equivalent tothe divergence Of the gradient of a scalar function, Objectives ‘Afier studying this chapter, you should be able to: ‘© write formulas for the partial derivatives and for the differential of a function if given a formula for the function and use these in applications such as the calculation of small changes in a dependent variable; «* perform a change of independent variables and obtain formulas relating different partial derivatives; ‘+ use identities involving partial derivatives to eliminate undesirable quantities from thermodynamic formulas; « identify an cxact differential and an integrating factor; ‘¢ find constrained and unconstrained maximum and ‘minimum values of functions of several variables; ‘* form the gradient, divergence, curl, and Laplacian of any relatively simple function 8.1 FUNCTIONS OF SEVERAL INDEPENDENT VARIABLES ‘A function of several independent variables gives the value of @ dependent variable if you specify a value for each of the independent variables. The equilibrium thermodynamic properties of a fluid (gas or liquid) system of one substance and one phase are functions of three independent variables. If we choose a set of values for the temperature, T, volume, V, and amount of the substance in moles, n, then the other thermodynamic properties, such as the pressure, P, and the 89thermodynamic energy, U, are functions of these variables, ‘We can write P= PTV .n), U =U Vn) (Bla) 2) ‘We can choose any three of the variables as independent variables so long as at least one of them is proportional to the size of the system, and the other variables are then ‘dependent variables that depend on the three independent variables that we chose. A variable that is proportional to the size of the system is called an extensive variable. We could also write vu =um Pn, U=UPV an), (83a) (8.30) and so on. A variable that is independent of the size of the system is called an intensive variable. If we consider only intensive variables, only two variables are independent, ‘The molar volume, defined as V/n, is the quotient of two extensive variables, and is an intensive variable, as are the temperature and the pressure, The pressure ofa fluid system cof one substance depends only on the temperature and the molar volume. ‘We assume that the functions that represent he behavior of physical systems are piecewise continuous with respect to each variable, If we temporarily keep all but one of the independent variables fixed, the function behaves as 1 piecewise continuous function of that variable. We also assume thatthe functions are piecewise single-valued. That is, except at isolated points, there is one and only one value of the dependent variable for a given set of values of the independent variables. If the temperature of a gas is fairly high and its volume is large enough, the pressure of a gas is given to a good approximation by the ideal gas equation RT P= PO Vn) =F Ba) where Ris the ideal gas constant, equal to 8.3145 J K-! mol! or 0.082061 atm K-! mol Tis the absolute temperature, and Vm is the molar volume. jure 8.1 shows the dependence ofthe pressure ofa nearly ‘gas as a function of the molar volume at several fixed {emperatures, With only two axes on our graph, a curve can show the dependence of P on Vey only fora fixed value of 7. ‘Three-dimensional graphs can show the dependence of a dependent variable on two independent variables, but are much more difficult to use, since we have only two- dimensional paper and two-dimensional computer screens. Figure 8.2 is a perspective view of a three-dimensional graph representing P as a function of Vy and 7: The value of P is given by the height from the horizontal plane to Mathematics for Physical Chemisty 5x 105 patna 1108 ° 0.05 on Vo (m8 mot) FIGURE 8.1. The pressure ofa nearly ideal gas a function of Vi for several vals of 7 I 5x 105 FIGURE 8.2: The pressure ofa neatly ideal gs function of Vigan T. surface, which plays the same role as the curve in & ‘two-dimensional graph. Itis fairly easy to read quantitative information from the two-dimensional graph in Figure 8.1, but the perspective view in Figure 8.2 is more difficult fo read numbers from. If you have more than two independentCHAPTER | 8 Differential Calculus with Several Independent Variables variables, a graph cannot be visualized. Sometimes attempts are made to show roughly how functions of three variables depend on their independent variables by drawing ‘8 perspective view of three axes, and then tying to communicate the approximate value of the dependent variable by @ density of dots placed in the diagram or by ‘contours of equal values of the dependent variable. Tables of values are also cumbersome with two or more independent variables, since @ function is now not a set of ordered pairs of numbers but a set of ordered sets of three ‘numbers of four numbers, and so on. For two independent variables, we need a rectangular array, with values of one independent variable along the top and values of the other along one side, and values of the dependent variable in the body of the array, For a third independent variable, we would need a different sheet of paper for cach value of the third variable. The most common way to represent a func: tion of several variables is with a mathematical formula. 8.2 CHANGES IN A FUNCTION OF SEVERAL VARIABLES, PARTIAL DERIVATIVES piston and a valve through which gas can be admitted dP av dT fixed) 8.5) ara(2)av omar ined, 0s 86) ap. ap=(22) av (and fixed), a) nr ‘The quantity (@P/4V)q.r is called the partial derivative of P with respect to V at constant n and 7. The partial erivative is obtained by the differentiation techniques of Chapter 6, treating n and T like ordinary constants. We @ ccan also keep another set of two of the three independent variables constant. There are as many partial derivatives of a given function as there are independent variables on which it depends. If the gas is adequately described by the ideal ‘gas law, these derivatives are (3),,.- GFF), RT =- SF mand T fixed), 6:7) (#2) (a a). ° Grlr]),, = “ (n and V fixed), (8.8) aP\ @ [nRT (2), GF), =F rani vine, 9) Each of these partial derivatives is obtained by the usual differentiation technique, treating the other variables as constants, 8.2.1 Differentials If we make an infinitesimal change dV in the volume and ‘a change dT in the temperature of the gas while keeping fixed, the change in the dependent variable P is the sum of two expressions like that in Eq. (8.6). dP ar av a ar fixed). (8.10) = (ar), 07+ FH), ot med. G10 If we make the changes dV in V, d7'in 7, and dn in n, these cchanges affect P separately, and we can write for the total infinitesimal change in the dependent variable P, ap (3) av (3) ar+(Z) an WY ar) * an) py on The infinitesimal change dP given by this expression is called the differential of P, or sometimes the total differeniol of P. Each term gives the effect of one independent variable with the other independent variables treated as constants I we have a dependent variable y that depends on 1 Independent variables, x12, 83...» Sys its differes f-E G). where the subscript x” stands for keeping all ofthe variables except for x; fixed in the differentiation, This equation issometimes called the fundamental equation of differential calculus. ‘The expression for dP for an ideal gas is RT aR av + ap (8.13) For small but finite changes, an approximate version ofthis equation can be writen, mRT nk ap~ "Fave RT AT+ ‘An (8.14) Example 8.1. Use Eq, (8.14) to caleulate approximately the change in pressure of an ideal gas if the volume is changed from 20,0001 to 19.8001, the temperature is changed from 298.15 K to 299.00 K, and the amount of gas in moles is changed from 1.0000 mol t 1.0015 mol. Com- pare the result with the corect value ofthe pressure change. Using the fact tat in SI units the value of the ideal gas constant, R, is equal (0 8.3145 J K~! mol~!, 4.0000 mol)(8.3145 1K“! mol=!)(298.15 K) (0.020000 m) x (-0.200 «10° m) APS (1.0000 mol) (8.3145 JK! mot~) 5 * 0:020000 m* (085K) (8.3145 K-! mol} 298.15 K) Sao (0.0015 mot) © L779 x 10° Nm? = 1.779 x 10° Pa, Where we also used the fact that 1 J=1Nm, The actual change is mRTy _ mRT Ve Vi = 1,797 x 10° N m=? = 1.797 « 10° Pa. AP =~ P= ur approximate value is in error by about 1%. In this example the exact calculation could be made ‘more easily than the approximation. However, in physical chemistry itis frequently the case that a representation of a function is not known, but values for the partial derivatives are available, so that approximation can be made while the exact calculation cannot. For example, there is usually no simple formula giving the thermodynamic energy as afunc- tion of its independent variables. However, we can write au = (2), ar (22) ar (2) aT) py BP) ry an) pr (8.15) Espen aes of thee pt dies ae frequently available, so that even if we have no Mathematics for Physical Chemisty representation of the function giving a value of U, ‘we can compute an approximate value for AU. wo (),.970 (3), oF) (8.16) Example 8.2. For a sample of 1,000 mol (0.15384 kg) of liquid carbon tetrachloride (CCL) ata temperature of 20 °C and a pressure of 1,000 atm, the following experimental values are available: (2) = 12947 K7! T) oy 000 mol of CCl, if 10 40,0 °C and its Estimate the change in the energy of its temperature is changed from 20.0 pressure from 1.0 atm to 100.0 atm. Since m is fixed, AU © 129.41 K7')(20.0 K) + (851 «10-4 an) 080m) = 2588 J + 0.084 J = 2588 J Notice that the second term is negligible. Exercise 8.1. iven by The volume of a right circular cylinder is Vaxrh where r is the radius and h the height. Calculate the percentage error in the volume if the radius and the height are measured and a 1.00% error is made in cach ‘measurement in the same direction, Use the formula for the differential, and direct substitution into the formula for the Volume, and compare the two answers. 8.3 CHANGE OF VARIABLES We can consider the thermodynamic energy U of a one~ ‘component, one-phase system tobe a function of 7, V, and n, usurVn) 7) ora function of 7; P, and n, U=UP 0») (8.18) ‘The two choices lead to different expressions for dU, w= (Fe), 8°* (Ee), 0” Gr) (8.19)CHAPTER | 8 Differential Calculus with Several Independent Variables and aw aw aw w= (FF), 2+ (3),,0°* Ge), (8.20) “Tete ae two diferent derivatives of U with espeet to 7: (@U/aT)y.» and (8U/8T)p,y. For most systems, these Example 8.3. Express the function : = x(x,y) = ax? + xy +e)" imterms of rand u, where w = xy. Find the two partial derivatives (82/8x)y and (22/8%)« 8.4 USEFUL PARTIAL DERIVATIVE IDENTITIES Its fairly common in thermodynamics to have measured values for some partial derivative such a8 (0H /2T) pin. which is equal to the heat capacity at constant pressure. However, some other partial derivatives are difficult or impossible to measure. Itis convenient to be able to express such partial derivatives in terms of measurable quantities ‘We now obtain some identities that can be used for this purpose. 8.4.1 The Variable-Change Identity Inthe previous example, we had the formulato represent the ‘mathematical function, In thermodynamics, iis unusual to have a functional form, We will obtain a formula ofthe type aU (= > (F),.- G),..* where the question mark indicates a tert that we need to find. The procedure that we use isnot mathematieally acceptable but it does give the conect answer To constuct the paral derivative onthe letchand sie of our equation, we begin with an expression forthe differential JU that Contains the deiative on the right hand side. This is the Same as Ea (8.20) We"divide” this ferential expression by d7, specifying that we keep V and n constant, because the deivative we wanton thelet-hand sie is (BU /3 (8.21) D This “division” cannot be done legitimately, because a7 is an infinitesimal quantity, but it will lead to the correct ansee We ge ww (su) ar, (au) ar (au) te a ~(sr),,a* (ae), a7 * Gn) par (2) We interpret the “quotients” as partial derivatives, since we hhave specified that we want to have V and n constant. The same variables must be held fixed in all four of the partial derivatives (o keep a valid equation. We now write (Fr),,~ Gr),.AG),.* Gr) G7),, “GF. cof 1 with respect to anything is zero if n is constant, so we have (),.° (r),.* ), (Fv EE i dometant o (8.23) Example 8.4. Apply the foregoing method tothe function in Example 8.2 and find the relation between (@z/4x),, and (az/ax)y ),-@),-@).@), (2) bx + 2ey = bx 4 @)-[2@]--3 (8),<(@) 2 This agrees with Example 8.2, as it must. Exercise 8.2. Complete the following equations. @) FP = (Pye © (3).5=(BDawt? (© Apply the equation of part b if z = cos (x/u) + 4y/u and w = y/u.8.4.2 The Reciprocal Identity The reciprocal identity states that a derivative is equal to the reciprocal ofthe derivative with the roles of dependent and independent variables reversed: The same variables must be held constant in the two derivatives (8.25) Show that (F -—t_ BV) 7 OVT8P nt for an ideal gas. Example 8.5. at @V/8P)\n7 — —nRT/PP nRT (nRT/V) RT mRT V2 Exercise 8.3. Show that the reciprocal identity is satisfied by (82/@x), and (@x/22), if sa(?) and_x = ysin"! (2) = yaresin (z) 8.4.3 The Euler Reciprocity Relation There are two kinds of second partial derivatives. If 2 = z(x,y) we can differentiate twice with respect to x: Pe a (az ae)“ [ae ae), In this case y i held fixed in both differentations. In addition, we can also dferentate once with respect to x ‘and once with respect to y. This produces a mixed second artial derivative. az a (az ayo ~ [ay lar), | In the symbol on the left, the independent variable on the right operates firs. Since both variables are shown inthe symbol, the subscripts are usually omitted, asin the symbol on the left, However, i there is third independent variable, (8.26) (827) Mathematics for Physical Chemisty it must be held constant and is listed as a subscript, For example, (#),-[G9), J, is possible to differentiate in the other order, The Euler reciprocity relation is an identity relating the two mixed second partial derivatives. t was proved by Euler! that the {wo different mixed second partial derivatives must equal cach other: (8.28) 7 wy (8.29) ayer Example 8.6. Show (@P/av a7), =(@P/aT aV), for an ideal gas or) [8 (nk svat), Lav VW), (arr) arav), Exercise 8.4, Show by differentiation that (%2/@y x) = (efx ay) if that =e sin (x) 8.4.4 The Maxwell Relations ‘An important set of identities obtained from the Euler reciprocity relation and thermodynamic equations is the set ‘of Maxwell relations.? These relations allow you to replace ‘partial derivative that is difficult or impossible to measure ‘with one that can be measured. One of the Maxwell relations is obtained from the thermodynamic relation au =Tas— Pav (8.30) which holds for reversible changes in a closed system (one with fixed value of n, the amount of substance in the system). Use of the Euler reciprocity relation gives (),,--G), ‘Another relation is (),.- Gr) Wore VT) vm ‘Leonhard Euler (1707-1783) was a great Swiss mathematician who mae many eonribaions. The eter“ was chosen forthe bas of ral logarithms in his honor 2 James Clerk Maxwell (1881-1879) was great Scotish physicist who ‘made contributions to thermodynamics, but whose greatest contbuton ‘vas the Maxwell equation of eleeomagnetism. 31)CHAPTER | 8 Differential Calculus with Several Independent Variables ‘This relation ean be used to replace (28), by (32) gu which is much more easly measured. Thee sa mnemonic device thatcanbe used toconstructother Maxwell relations Write Sand Tin opposite comer of the relation, and P and Vin the other opposite comers. There are four ways to do this, Keep m fixed on both sides, and on each side keep the independent variable fixed that is differentiated on the other side, IF Tand V occur in the sume derivative, inser a negative sign on one side Example 8.7. Find an expression for (@8/8Vz,,) for an (r),.° °F This is an easily measured quantity. Exercise 8.5. Using the mnemonic device, write three additional Maxwell relations. 8.4.5 The Cycle Rule Another useful identity is the eyele rule (2... Many people are a frst surprised by this identity, thinking at first thatthe right-hand side should equal +1 instead of —1. We will “derive” this in the same nonrigorous way as, was used to obtain Eg. (8.24). We write the differential of yas a function of x and z: a= (2) seo (2) a (8.32) (8.33) (8.34) _(® 8 z bx a), We have used the fact that the partial derivative of x with respect tis equal to unity. We multiply both terms ofthis, D equation by (8.x/@y), and apply the reciprocal identity v= (2).(2),), Our derivation is indefensible, but the result is correct. (8.35) Example 8.8. For the function y = zln(x), show that the cele rule is valid. (Ay /Ax)z = z/x, (@x/a2)y == (@efayrs = 1/ln(x), (@y/Ax)<(8x92)y(B2/8y)« = G/xVe""* (—%) ante --e"() (as) = G)eeges Exercise 8.6. For the function y = x2/z, show that the cycle rile is valid. 8.4.6 The Chain Rule ‘The chain rule involves a variable that is function of an independent variable that itself is a function of another variable. If z = <(w,x,y) but if x ean be expressed as a funetion of u,v, and y, then ®-@.€ AY uw NAD wu This is very similar to Eq. (6.20). Notice that the same varsles mut be held Sted inal tee deatves (8.36) Example 8.9. Show that if 2 = ax? then Eq, (8.36) is valid, bwx and x = uy (2), (2), -e2-rho = 2m ow (F), = [se (ott tom) | = 200 haw Exercise 8.7. Show that if then the chain rule is valid, ax} +bsin (x) and x = ey 8.5 THERMODYNAMIC VARIABLES RELATED TO PARTIAL DERIVATIVES ‘The following are commonly measured quantities that are related to partial derivatives:¢ Heat capacity at constant pressure ‘¢ Heat capacity at constant volume (), =7(28) 7(2 yew voor), Aisha comprestily ry syle), =4(2) WaT) nn In these equations, U represents the thermodynamic energy, H represents the enthalpy, defined by H 14 PV and S represents the entropy, defined only through its differential Saree as = te where dgiev represents an infinitesimal amount of heat transferred to a system in a reversible process, There are a number of useful relationships among these quantities. Example 8.10. Show that Cp/Cy = er xs Using the cycle rule on the numerator denominator, and the Co _ (Dre _ ral Cr Gly = ral ePsn We use the reciprocal identity twice to write Ce cy a ks Mathematics for Physical Chemisty 8.6 EXACT AND INEXACT DIFFERENTIALS ‘The differential ofa function is called an exact differential. There can also be differential forms that are not differentials of any function. A general differential form or Pfaffian form in terms of dx and dy can be written du = M(x,y)dx + My dy, (837) where M and N are functions of x and y. If this is the differential of a function, then M and N must be the appropriate partial derivatives of that function, If M and NV are not the appropriate partial derivatives of the same funetion, du is called an inexact differential. Tt is an infinitesimal quantity that can be calculated from specified infinitesimal values of dx and dy, but it is not equal to the change in any function of x and y resulting from these changes. In order to tell whether some differential form san exact differential or not, we apply the Euler reciprocity relation, Ir there exists a function w = w(x,y) such that (22), sat ney=(2),. aa then from the Buler reciprocity relation, May) : axay Gyax’ 639) Equation (8.40) represents a necessary and sufficient condition for the differential of Eq. (8.37) to be exact. That is, if the differential i exact, Eq (8.40) will be obeyed, and if Eq, (8.40) is obeyed, the differential is exact. Example 8.11. exact Show that the following differential is Exercise 8.8, Determine whether the following differen- tial is exact, du = Qax + by?)de + (bry dyCHAPTER | 8 Differential Calculus with Several Independent Variables Differential forms with three or more terms can also either be exact or inexact. The Euler reciprocity relation provides a test for such differentials. For example, if du = M@x.v.z)dx + NQw.y.2)dy + Plx.y.z)dz, (841) then in order for this to be an exact differential, the three ‘equations must be obeyed (S).- Gi). @).- Ge 9 i Exercise 8.9. Show that the following is not an exact differential du = Qy)dx + (dy + 60s (z)dz ‘There are two important inexact differentials in thermodynamics. Assume that a closed equilibrium system undergoes an infinitesimal reversible process. (one in Which the system remains at equilibrium). We denote the amount of heat transferred to the system by dey and denote the amount of work done on the system by dey. ‘Thermodynamic theory implies that if no work is done ‘except by changing the volume ofthe system, then Pav, dite = (8.45) where P is the pressure of the system and Vis its volume. Example 8.12, Show that for an ideal gas undergoing a reversible process with n fixed, duscy is inexact. We choose T and V as our independent variables and write the differential form dw = MdT+NAV (0 fixed) Comparison with Eq, (8.45) shows that M = 0 and N = =P = —nRT/V. We apply the test for exactness, Fa, (8.40), using the fact that n is constant Gr),,-8 (),.-Lin-A*)I,, In thermodynamics, quantities such as the thermody namic energy, the volume, the pressure, the temperature, ‘the amount of substances, and so forth, are functions of the variables that can be used to specify the state of the system. They are called state functions or state variables D ‘The differentials of these quantities are exact differentials, Work and heat are not state functions. There is no such thing as an amount of work or an amount of heat in a system. We hhave already seen that duzey is not an exact differential. An infinitesimal amount of heats also not an exact differential For a system in which work is done only by changing the volume, the thermodynamic energy, U, is defined by its differential aU = dg +aw, ‘The first law of thermodynamics asserts that dU is an exact differential even though dg and dw are not Exercise 8.10, The thermodynamic ‘monatomic ideal gas is given by _3nRT 2 Find the partial derivatives and write the expression for dU using TV, and n as independent variables. Show that your differential is exact energy of a vu 8.6.1 Integrating Factors ‘Some inexact differentials produce exact differentials ifthe inexact differential is multiplied by a function called an integrating factor. Example 8.13. Show that the differential du = M dx +N dy = Qax? +bxy)de + (bx? +2exy dy is inexact, but that 1/x isan integrating factor, so that du / is exact. We first show that duis inexact: Bo 1 [Ree +bxy)| = bx ay ds = 2bx + 2ey # by y so duis inexact, Afler we divide by x, we obtain the partial derivatives [@)] Laem, [eC] eee] so (1/x)du is exact, [Zoe 2] Exercise 8.11. Show that the differential, xin(x) x? arses © Je y 9 is inexact, and that y/x is an integrating factor.“The second law of thermodynamics assent thateven though dle is not exact, the reciprocal of the Kelvin temperature is an integrating factor: va See so that dS, the differential ofthe entropy, is exact. ‘There is no general method for finding an integrating factor, although we will discuss a method that will work for a particular class of differential forms in Chapter 8, when we discuss differential equations, However, it ig true that if a differential possesses one integrating factor, there are infinitely many integrating factors for that differential, 8.7 MAXIMUM AND MINIMUM VALUES OF FUNCTIONS OF SEVERAL VARIABLES: A point at which either a maximum or a minimum value in a function occurs is called an extremum. For example, Figure 83 shows a perspective view of a graph of the function f = e~*¥*. The surface representing the function has a“peak" at the origin, representing amaximum value of the function, The figure also shows @ curve at which the surface intersects with a plane representing the equation y = 1—x. On this curve there is also a maximum, which has a smaller value than the maximum at the peak. We call this value a constrained maximum subject to the constraint that y = 1 — x. We discuss the constrained maximum later. io inf FIGURE 8.3 The surface representing the Function the absolute maximum anda constrained maximum showa. Mathematics for Physical Chemisty ‘The maximum atthe origin in Figure 8.3: called a focal ‘maximum or a relative maximum, because the value of the function at such a peak is larger than at any other point in the immediate vicinity. However, a complicated function can hhave more than one local maximum, Also, if we consider 4 finite region, the function might have a larger value somewhere on the boundary of the region that is larger than the value at alocal maximum. To find the absolute maximum of the function for @ given region, we must consider all local maxima and any points on the boundary of the region that might have greater values. The peak at the origin in Figure 8.3 is the absolute maximum of this function, Points of minimum value are completely analogous to points of ‘maximum value. Local minima are located at the bottom ‘of depressions ot valleys in the surface representing the function, To find an absolute minimum for a given region, ‘you must consider all local minima and any points on the ‘boundary of the region that might have smaller values. To locate a local maximum or minimum, we use the fact that the plane that is tangent to the surface will be horizontal at any local maximum or minimum, Therefore, the curve representing the intersection of any vertical plane with the surface will have a local maximum or a local minimum at the same place. The partial derivative with respect to ‘one independent variable gives the slope of the tangent to the curve in the plane corresponding to a constant value of the other independent variable, so we can find a local ‘maximum or minimum by finding the places where all the partial derivatives of the function vanish simultaneously. (Our method fora differentiable function of two variables is therefore to (=), (3), 2. Calculate the value of the function at all points satisfy- ing these equations, and at the boundaries of the region, being considered and any cusps or discontinuities. ‘The maximum or minimum value in the region being ‘considered must be in this set of values. (8.46) Example 8.14, Find the maximum value of the function shown in Figure 8.3, f = e-™™ Ata local maximum or minimumCHAPTER | 8 Differential Calculus with Several Independent Variables ‘The only solution for finite values of xandyis x = 0,¥ = 0. Since no restricted region was specified, we consider all values of x and y. For very large magnitudes of x or y, the function vanishes, so we have found the desired absolute maximum, at which (0,0) = L In the case of one independent variable, a local maximum could be distinguished from a local minimum or an infleetion point by determining the sign of the second Gerivative, With more than one variable, the situation is, more complicated. In addition to inflection points, we can have points corresponding to a maximum with respect to fone variable and a minimum with respect to another, Such a point is called a saddle point, and at such a point, the surface representing the function resembles a mountain ‘pass or the surface of a saddle. Such points are important in the transition-state theory of chemical reaction rates For two independent variables, we calculate the following quantity: >-(32) (5) -(H) ‘The different cases are as follows: (847) 1, If D > 0 and (8? f/x") > 0, then we have a local 2D > O and (f/x) < 0 thon we hve a ol 3, IF <0, then we have nthe s lea maximum nor 4, 11D =o, the tetas, and wecannotel what we have Exercise 8.12. Evaluate D at the point (0,0) for the function ofthe previous example and establish thatthe point is a local maximum, For more than two independent variables, the method is similar, except that there is one equation for each independent variable. Sometimes we must find a maximum or a minimum, value of 2 function subject to some condition, which Such an extremum is called constrained maximum ot a constrained minimum. Generally, @ constrained maximum is smaller than the unconstrained maximum of the function, and a constrained ‘minimum is larger than the unconstrained minimum of the function. Consider the following example: is called a constrain. Example 8.15. Find the maximum value of the function in the previous example subject to the constraint x + y = 1 D The constraint corresponds to the specification of yas a funetion of x by yeas This function is given by the line in the x-y plane of Figure 8.3, We are now looking for the place slong this ccurve at which the function has a larger value than at any other place on the curve, Since y isa function of x on the curve, the direct way to proceed is to replace y by 1 — x fal =f) = Since fis now a function only of x, the local maximum is now at the point where df /dx vanishes: af a 2-0 - 4x42) This equation is satistied by x = 4 and by [x] > 90 The constrained maximum corresponds to x = } and the minimum corresponds to |x| —> 20. AC the constrained maximum y = 1— }—/} and the value ofthe function at the constrained maximum is ‘As expected, this value is smaller than the unconstrained maximum, at which f = 1 8.7.2 Lagrange’s Method of Undetermined Multipliers? If we have a constrained maximum or minimum problem with more than two variables, the direct method of substituting the constraint relation into the function might not be practical. Lagrange’s method finds a constrained ‘maximum or minimum without substituting the constraint relation into the function. Ifthe constraint is written in the form g(x,y) = 0, the method for finding the constrained ‘maximum or minimum in f(x,y) is as follows: 1, Form the new function (x.y) = fly) +Agte 9. (8.48) where 4 is aconstant called an undetermined multiplier. Its value is unknown at this point of the analysis. 5 Named for Joseph Lous Lagrange (born GuiseppsLadovieo Lageangi), 1736-1813, French-talian physicist and mathematician2. Form the partial derivatives of u, and set them equal to © (,-@,208) <0 (2) - (2) Solve the set of equations consisting of ¢ = 0 and these ‘wo equations as a set of simultaneous equations for the value of x, the value of y, and the value of that correspond to the local maximum or minimum, (8.50) Example 8.16. Find the constrained maximum of the previous example by the method of Lagrange. ‘The constraint equation is written stay) axtyn ‘The function u is u(ey) =e bt “The three equations to be solved are geayaxtyn =0. We begin by solving for 2 in terms of x and y. We multiply the first equation by y and the second equation by x and add the two equations, The result can be solved to give xy Substitute this into the first equation to obtain (arene 4 The exponential factor is not zero for any finite values of x and y, so When the expression for A is substituted into the second equation in the same way, the result is The difference of these two equation is -2x+2y =0, Mathematics for Physical Chemisty which is solved for y in terms of x to obtain This is substituted into the third simultaneous equation to obtain xtra which gives 1 aa ‘This is the same result as in the previous example. In this cease, the method of Lagrange was more work than the direct ‘method. In problems involving more variables, the method of Lagrange will usually be easier. Exercise 8.13. (@) Find the local minimum of the function S(x,y) =a? +9? +2 (b) Without using the method of Lagrange, find the constrained minimum subject to the constraint, ra-y (©) Find the constrained minimum using the method of, Lagrange. ‘The method of Lagrange also works ifthere is more than fone constraint, Assume that we desire the local maximum (or minimum of the function f= S92) sD subject to the two constraints giz) =0 (8.52) and. g2(ey,2) = 0. (8.53) ‘The procedure is similar, except that two undetermined ‘multipliers are used. One forms the function u = ulry.2) = fay.2) + Agi Oey.2) + 22g0(0,9.2) (8.54) and solves the set of simultaneous equations consisting of Eqs. (8.52) and (8.53), and the three equations: (8.55) (8.56) 57)CHAPTER | 8 Differential Calculus with Several Independent Variables Tor The result is @ value for 2), a value for Aa, and values for x.y, and z which locate the constrained local maximum Example 8.17. Find the minimum in the function fax subject to the constraints +Ay =D +42 (2-2) We need to solve the equations (@),.-4 au (#)__-2™ MY) nati=o, (2), plus the (wo constraint equations. This is a simple case, since the first equation gives =0 and the constraint equations give the values of y and z. The constrained minimum occurs at x=0, y= ‘The value of the function at this point is f= Exercise 8.14. Find the minimum of the previous example without using the method of Lagrange 8.8 VECTOR DERIVATIVE OPERATORS An operator is a symbol standing for one or more mathematical operations to be performed on the function represented by the symbol to the right of the operator symbol. There are several vector derivative operators that apply to functions of three or more variables, 8.8.1 Vector Derivatives in Cartesian Coordinates Cartesian coordinates in three dimensions are more easily visualized than other coordinate systems, since we are naturally familiar with notions of east-west, north-south, and up-down, correlated with x,y, and z coordinates, The Gradient If fis some scalar function of x,y, and z, the gradient of f is defined in Cartesian coordinates by )ate)aejmn ss where i, j, and Kk are the unit vectors in the directions of the positive ends of the x,y, and z axes, respectively. The gradient of f is sometimes denoted by grad f instead of Vf. The symbol V, which is an upside-down capital Greek delta, is called “del.” The gradient of a scalar function is a vector function, At any given point in three-timensional space, the direction ofthe gradient ofa scalar function is the direction in which the function is increasing most rapidly, and its magnitude is the rate of change of the funetion in that direction, (definition) Example 8.18, Find the gradient of the function Paygareyed (2) a2) a + jy + K2z = 2h + jy + ke), ‘The function f = x? + y? + 2? is spherically symmetric. ‘Thats, ithas the same value at all points that are the same distance from the origin, At any point this gradient is a vector pointing directly away from the origin, which is the direction in which the function increases more rapidly than in any other direction. Exercise 8.15. Find the gradient of the funetion ax} + yer aQy.z) where a and b are constants. A common example of a gradient is found in classical ‘mechanics. the force on aparticle is velocity-independent, itis given by F=-wW (8.59) where V is the potential energy of the system and F is the force. The gradient is taken with respect to the coordinates of the particle being considered, and the coordinates of any other particles are (reated as constants in the differentiations Example 8.19, Neglecting the attractions of all other celestial bodies, the gravitational potential energy of the cearth and the sun is given by Gmgme v=where G is the universal gravitational constant, equal to 6.673 x 10-"! ms? kg“, me is the mass of the sun, me is the mass ofthe earth, and ris the distance from the center of the sun to the center of the earth, ra(dastee) xpress forceon the earhinCaesian coordinates That isbn th foe interme te unit eco and th the components expressed in terms of x.y, and z. Expressing rin terms of x, y,and 2 - oom (Fr) a(Gaaar) “(Aa)] om) -onol( 3) 38) 4) Grane, orn where ris the position v ix by + kz, Exercise 8.16. The average distance from the center of the sun to the center of the exrth is 1.495 x 10! m, The mass of the carth is 5.983 x 10% kg, and the mass of the sun is greater than the mass of the earth by a factor of 332958, Find the magnitude of the force exerted on the earth by the sun and the magnitude of the force exerted on the sun by the earth, The Divergence The operator V (“del”) can operate on vector functions as well as on scalar functions. The gradient of a vector Mathematics for Physical Chemisty function bas nine components, since the function has three ‘components and the operator has three components. Such ‘a quantity is called a dyadic, and we will not discuss it. ‘We will discuss two vector derivatives, one of which is somewhat analogous to a scalar product of two vectors, and cone of which is somewhat analogous to a cross product of two vectors. An example of a vector function isthe velocity of a compressible flowing fluid, which depends on time as ‘well as on position. Ata fixed time, we write v=v(u.y.2) (8.60) In terms of Cartesian components, eX y.2) + fry eay.2) + keel, Bol) The vergence of vector function Fis defied in Cartesian coordinates by Tak) (3), oh wre (F)(G)+) 6.02) here F isa vector funtion wth Cartesian components F.oFy, and F. The divergence ofa vector function F isa scalar and is somewhat analogous to a scalar product (dot product) of the del operator and a vector. The divergence of Fis sometimes denoted by div ‘One way to visualize the divergence of a function ist consider the divergence ofthe velocity of « compressible fluid. Curves tat are followed by small portions ofthe fluid are called seam lines. In aFegion where the seam Tins diverge (become father from each eter a the ow is followed, the Mud will become less dense, and in such 2 region the divergence ofthe velocity is positive. The divergence thus provides a measure ofthe spreading of the stream ies, The equation of contin of «compressible fluid expresses the effec this spreading has on the density of the Mud, which depends on postion and on ime. The lefinition),. V-oy=- (8.63) where p is the density of the fluid, vis its velocity, and ris the time, Example 8.20. Find V -F if F is given by a Fai? tiyeth y 2xz V-Fa2rt24 y Exercise 8.17. Find V-r where tiy tke.CHAPTER | 8 Differential Calculus with Several Independent Variables The Curl Another derivative of a vector function is the curl. The ccurl of the vector function F is defined in Cartesian ‘coordinates by (definition) (8.64) ‘The curl is a vector and is somewhat analogous to the vector product (cross product) ofthe del operator and a vee~ tot. To remember which vector derivative is which, remem- ber that “dot” and “divergence” both begin with the letter I and that “cross” and “curl” both begin with the letter The symbol curIF is sometimes used for the curl of F. ‘The curlofa vector function is more difficult to visualize than is the divergence. In fluid flow, the curl of the velocity gives the vorticity of the flow, or the rate of turning of the velocity vector. Because of this, the symbol rotF is also sometimes used for the curl of F Example 8.21. Find V x Fift Fiytje+ke, Vx F=i-1)+jO-D+kO-1) = Exercise 8.18, Find V x rif ix iy tke. Explain your result The Laplacian ‘The Laplacian is defined asthe divergence of the gradient If Fis a scalar function, its gradient is a vector and the divergence of the gradient of f is a scalar. In Cartesian coordinates the Laplacian of a sealar function f(x,y.2) is given by GE (efinition) (8.65) ‘The operator V - V is called, the Laplacian operator! and has its own symbol, V2, sometimes called “del squared.” This operator occurs in the Schrédinger equation of quantum mechanics and in electrostaties. * After Piewe Simon, Margus d= Laplace, 1749-1627 famous French mathematician and atronomer, 03 Example 8.22, Find the Laplacian of the function f (x,y,z) = Asin (ax) sin (by) sin (cz) Vv? f = —Aa® sin (ax) sin (by) sin (cz) — AB? sin (ax) sin (by) sin (cz) —Ac? sin ax) sin (by) sin (2) =-A (@ ie 2) sin (ax) sin (by) sin (cz) =-(@ +042) F Exercise 8.19. Find the Laplacian ofthe funetion frexpir ty t2yae™ Two other possibilities for successive operation of the del operator are the curl of the gradient and the gradient of. the divergence .‘The cut ofthe gradient of any differentiable sealar function always vanishes, Exercise 8.20. Show that V x Vf differentiable scalar function of x,y, and z Oi fisa 8.8.2 Vector Derivatives in Other Coordinate Systems Coordinate systems such as spherical polar or cylindrical polar coordinates are called orthogonal coordinates, because an. infinitesimal displacement produced by changing only one of the coordinates is perpendicular (orthogonal) toadisplacement produced by an infinitesimal change in any one of the other coordinates, Figure 8.4 shows displacements, drawn as though they were finite, produced by positive infinitesimal changes in the spherical polar coordinates r,0, and 6. These displacements are denoted by ds; ,dsg, and dsp, and each one has the dimension of length, sy = displacement in rdirection = dr, (8.66) dsp = displacement in 6 direction = rd0, (8.67) 45g = displacement in 6 direction = r sin (8) 40 6.68) We define three vectors of unit length in directions of | the infinitesimal displacements in Figure 8.4, called e,es, and ey. An infinitesimal vector displacement is the vector sum of displacements in the three orthogonal directions. In Cartesian coordinates, ae =ide + jdy 4 hed. (8.69) In spherical polar coordinates, dr = er +eardd + egrsin(0)d9. (8.70)& \ ‘ Z FN ds=r sin) d6 FIGURE 8.4 Tsiiesimal displacements ds, dy, and dry produced by infinitesimal increments dr, d2, and d. We can write an expression for an infinitesimal vector displacement dr in a form that will hold for any set of orthogonal coordinates, Let the three coordinates of an comthogonal system in three dimensions be called 41,92, and qs. Let the displacements due to the infinitesimal increments be called dsy.dsp, and dss. Let the unit veetors in the directions of the displacements be called e),e2, and 5. The equation analogous to Eq. (8.70) is dr = €; ds + e2dsp +65 dss = €1 hy dgy +2 ho das +esha ds, 71) Where the ’s are the factors needed to give the correct expression for each displacement. For Cartesian coordinates, all three of the h factors are equal to unity For spherical polar coordinates, hy = I,ho = r, and h, r'sin (8). For other systems, you can figure out what the h's ate geometrically so that ds; = hy day for each coordinate, The Gradient The gradient of a scalar function f is written in terms of components in the direction of e1.e3, and e as vraeth rath vet (8.72) Bn Sy (873) Mathematics for Physical Chemisty TThe expression forthe gradient of afunction of spherical polar coordinates is ar or lar ae 798 + +r sin (a) a6 vf= 7) Exercise 8.21. (a) Find the h factors for cylindrical polar coordinates. (b) Find the expression for the gradient of a function of cylindrical polar coordinates, f = f(p,.2). (6) Find the gradient of the function f= eH in (6) The Divergence ‘The divergence of a vector function can similarly be expressed in orthogonal coordinates, If F is a vector function, it must be expressed in terms of the unit vectors of the coordinate system in which we are to differentiate, Fook teh ters (8.75) ‘The components Fj, F2, and Fy are the components in the directions of e).e2, and es, TThe divergence of the vector function F is given by __t lihahy + Uhh) aay fils VE a a [eam + (Blihs) at on B76) Example 8. (a) Write the expression for the divergence of a vector function F expressed in terms of spherical polar coordinates, + Fin@) 86” (b) Find the divergence of the position vector, which in spherical polar coordinates is reer ver Lia pir +040=3 Exercise 8.22, Write the formula for the divergence of a vector function F expressed in terms of cylindrical polar coordinates. Note that e; is the same as k.CHAPTER | 8 Differential Calculus with Several Independent Variables The Curl ‘The curl of a vector function F is defined by +e Taha In spherical polar coordinates esor) - Zen] mrs sin @) [39 1 fay 8 . emg [tel Arion) ten 8 +t [Sem 3(6)| Example 824 er sin (@) (8.78) Find the curl of the function F = V x ersin(@) = ey aaldno] rsin (@) Lag” ipa ~ est | Asin «| cos (¢) ~ OF Sin (@) The Laplacian ‘The expression forthe Laplacian ofa scalar function, is “ama (EE a (thes) a (si224)] hz 8q2 aga \ ha aga In spherical polar coordinates ede (Pepe Par ar Lar 7 sin? (0) 397 BRO) Example 8.25, Write the expression for the Laplacian in cylindrical polar coordinates For cylindrical polar ‘coordinates, iy = I,hy =r, and hy; wre iL ae) +a 5) *(%)) Exercise 8.23. Write the expression for the Laplacian of the function -” 10 PROBLEMS 1. Acrtainnoidel sass described by the equation of ame se ny, BT ** Vag where Tis the temperature on the Kelvin scale, Vi is the molar volume, P is the pressure, and X is the gas ‘constant. For this gas, the second virial coefficient Ba is given as a function of Tby sy = [-1.00. 10° = (2188 10 x e860] m mol"! Find (@P/@Via)r and (@P/@T)v,, and an expression for dP. 2, For a certain system, the thermodynamic energy U is ‘given as a function of S,V and n by U SUS, V in) = Kn BVP8 8/308 where Sis the entropy, Vis the volume, isthe number of moles, K is a constant, and R is the gas constant (a) According to thermodynamic theory, T = (BU /88)v Find an expression for (@U/98)v.n (b) According to thermodynamic theory, the pressure P = ~ @U/AV)s». Find an expression for (@U/AV)5.n (6) Find an expression for (2U /8n)s,v (d) Find dV in terms of dS,4V, and dn, 3. Find (@f/8x)y, and (@F/ay), for cach of the following functions, where a, b, and c are constants. (a) f =aryin) ) f =esin (xy Find (@f/8x)y, and (@f/ay)x for each of the following functions, where a, b, and c are constants. @ f=e+y/e+n. (b) f = (ax + by), S. Find (@f/@x)y, and (@f/y)x for each of the following functions, where a, 6, and c are constants. (a) Ff = acos* bry) 0) f =a0xp(—be? + 92). 6 Find (02f/@x%)y, (@f/2xdy), @F/Ayax), and (8/42), foreach of the following functions, where 4, band ¢ are constants @ fees @) f =cos (sy).7. Find (@f/8x7)y, (@f/axdy), (@f /Ayax), and (@F/ay4), foreach ofthe following functions, where 4, b, and c are constants. £ f= nx? + glory?) oy) 8 nd (92 /8x7)y, (2 f/8xdy), (82 /ayax), and (0 //4y°), foreach ofthe following funetion, where 4,8, and care constants @ f=+y 1 (b) f= sin (xy). 9. ‘Test each of the following differentials for exactness. (@) du = sec? (xy)ax + tan (xy), (b) du = ysin (xy) dx + xin (xy) dy. 10. ‘Test each of the following differentials for exactness (@) du = Bede — tan“! (dy, (b) du = (x? + 2x + I)dx + (y? + Sy + 4)dy. 11. ‘Test each of the following differentials for exactness. (a) du = xydy +xydy, (b) du = ye de 4 xe dy 12, If'u = RT In (aTVn) find dw in terms of dT, dV, and ddn, where R and a are constants. 13. Complete the formula (zr),.- Gr), 14, Find the location of the minimum in the function Fa Sey considering all real values of x and y. Whats the value of the function at the minimum? Mathematics for Physical Chemisty 15, Find the minimum in the function of the previous. problem subject to the constraint x + y = 2. Do this, by substitution and by the method of undetermined multipliers 16, Find the location of the maximum in the function, f= fey) =x? 6x + By ty? considering the region 0 < x <2and 0 < y <2 ‘Whats the value ofthe function atthe maximum? 17. Find the maximum in the function of the previous problem subject to the constraint x + y = 2. Do this by substitution and by Lagrange’s method of undetermined multipliers. 18, Neglecting the attractions of ll other celestial bodies, the gravitational potential energy of the earth and the sun is given by pee Gre Where G is the universal gravitational constant, equal to 6.673 x 107"! m! s~? kg~!, m isthe mass of the sun, me is the mass of the earth, and ris the distance from the center of the sun to the center of the earth. Find an expression for the force on the earth due to the sun using spherical polar coordinates. Compare your result with that using Cartesian coordinates in the example in the chapter. 19, Find an expression for the gradient of the function fo ) = c0s (xy) sin 20, Find an expression forthe divergence ofthe function F = isin? (x) + jsin® (9) + ksin? @), 21, Find an expression forthe Laplacian ofthe function J = 9? sin (@) 60s ().on \ Chapter 8 ) Differential Calculus with Several Independent Variables EXERCISES Exercise 8.1. The volume of a right circular eylinder is, given by Venn, where r is the radius and h the height, Calculate the percentage error in the volume if the radius and the height are measured and a 1.00% error is made in each ‘measurement in the same direction. Use the formula for the ifferential, and also direct substitution into the formula for the volume, and compare the two answers. v arth Ph rh = 2(0.0100) + 0.0100 = 0.0300 "The estimated percent error is 3%, We find the actual percent error: V2= Vi _ 272(1.0100)74(1.0100) rr? uo ah aPh = (1.0100)? = 1 = 1.03030 — 1 = 03030 percent error = 3.03% Exercise 8.2, Complete the following equations. +), Gr," (Gr),,~ G#)..* Gr), Gr), Mute fe Phys Chery ps0 0114802 0 (&),,-( )..G@)., cc. Apply the equation of part b if 2 = z(x.y.u) = cos (x) + y/u and w= y/u (),,° 2(4,u,w) = c0s (2) + (Zs 66." (%),,.@),, 1)=(&),, Exercise 8.3. Show thatthe reciprocal identity is satisfied by (@¢/8x) and (82/82), if essin(2) and x= ysl! (@ = yaesin(o From the table of derivativesMathematics fr Physical Chemisty where we have used the identity z(u.v.y) = a(uuy)? + bu sin) so 400% (22), =2a?y sano Exercise 84. Show by ferentiation that (2/298) = stu».x) = ax? + busin (2) @e/axayyit a we zoe sin. (3), <20+ Heo (S) 6). 2auvx + bu cos (y) = 2auv?y + bu cos (y) = & [xy sin (x) +x c05 (2)] +e? sin @)] aa, Exercise 88. Determine whether the following differen- ae ew tial is exact: = €? sin (2) + aye” sin (2) + xe" €08 (8) du = Qax + by?)dx + bxypdy = e [xy sin (x) +x €05 (2)] +e sin @)] Exercise 85. Using the mnemonic device, write three sar + by?) additional Maxwell relations. ae) = dby ary _ (av OP) 5, \OS) yn (8) --() The ei stn BP) nn \BT) nw (8), -(2) vere 89, Show thatthe following isnot an exact av Pra differential du = 2y)dx + (x)dy +08 (2)de. 10) face eta 7 8s be (222) =2 meth , () o (2), There is no need to test the other two relations. Exercise 8.10. The thermodynamic energy of a mona ‘omic ideal gas is given by 3nRT 2 Find the partial derivatives and write the expression for dU using 7, V, and n as independent variables, Show that your differential is exact. Gr),.° r),.=° Exereise 8.7. Show that if 2 = ax? + bu sin (y) and x = aw BRT vy then the chain rule is valid. Fa), inCHAPTER In 3RT AS) ar+cav + (>) dn Exercise 8.11. Show that the differential eae pe A js * y yl? is inexact, and that y/x is an integrating factor. carn =o axing) 27) _ may 1, 2x Re eS] = BOB 40 aly *yJay tyty “The new differential is Lex 2D ae + tin +xldy (2+y)ar+ tne + say wy Glin) +a Exercise 8.12, Evaluate D at the point (0,0) for the function of the previous example and establish that the point is a local maximum, 8 Differential Calculus with Several Independent Variables oot = ay? = 2e7 2 . (2 +) = -2ye8 (20) Sry aay AL(0,0) D=(-2(-2)-0=4 (34) Since D > 0 and (87f/8x7)y ~ 0, we have a local 2 Exei function e813, a. Find the local minimum in the Sees Aca relative extremum, (.-» (2) ,-» = (i6)~« Atthe extremum, 2+2=0 2 =0 mceopss 0-20 (8 vonage nent att f(=1.0) = (= 17 +2(- b, Find the constrained minimum subject to the constraint xty=0. (On the constraint, x Substitute the con: straint into the function, Call the constrained function Gy). 8G.y) =? + (— a)? 42x = 2x? 428 BagcseAt the constrained relative minimum, x=-1/2, y=12 ‘The value of the function at this point is in FO-WRAD = 4 +g - 20/2) = . Find the constrained minimum using the method of Lagrange. ‘The constraint can be written geyaxty=0 so that u@.y) =P $y? +20 44049) teu esha (22), ‘This vanishes at y = 4, which is outside our region, ‘Test the endpoint of this part of the boundary that we hhave not already tested: fQ.2)=4-1241644=12 ‘We have tested the four corners of our region and have found the maximum at (0,2). Check the final side of, ‘our region This vanishes at x = 3, which is outside our region, ‘The maximum of our function is (0.2) and is equal 1020, Find the maximum in the funetion of the previous. problem subject to the constraint x + y Fy) = 3? = 6x +849? We replace y by 2 — F(x) = x? — 6x 82-2) +Q-x)* =P = 6x 16 +84 $22 tx? = 2714 4 f aay a‘This vanishes at x = 0, corresponding to (0,2), which is on the boundary of our region. This constrained ‘maximum must be at (0,2) or at (2,0). The value of the function at (0,2) is 20 and the value at (0,2) is 20. ‘This is the same as the unconstrained maximum, 18. Neglecting the attractions of all other celestial bodies, the gravitational potential energy of the earth and the sun is given by Gmgme ye where Gis the universal gravitational constant, equal 10 6.673 x 107!! ms kg", mi is the mass of the sun, me is the mass of the earth, and ris the distance from the center of the sun to the center of the earth Find an expression for the force on the earth due 0 the sun using spherical polar coordinates. Compare your result with that using Cartesian coordinates in ‘the example in the chapter. --o(S8) = ( --= (4) Gmgme 2 F This agrees with the result of the example. 19, Find an expression for the gradient of the function (E942) = c0s (xy) sin (2) Vs = —iysin (xy) sin (@) + jxsin (xy) sin (@) +k 608 (xy) €08 (2) 20, Find an expression for the divergence of the function F = isin? (x) + § sin? (9) + sin? (2) VF = 2sin(x) cos (x) + 2sin (y) 608 (9) +2sin (2) cos (2) Mathematics for Physical Chemisty 21, Find an expression for the Laplacian of the function 1? sin (@) cos (9) v/==h2 (eLearn) me sin (8) 38 + 1 a sin? (8) 8g? 2sin (@) cos (9) [x0 ©) an sin (@) cos | ? sin @) cos (@) 7 wy 1? cos ($) 8 Fain ay ap it 0) 08 0)1 2 sin (0) €08 (@) = 6(sin (8) cos (8) £05) + Sin) [cos? (6) — sin? (0)] Sapo) cos? (0) c0s (6) sin £08 (@) 7) cos? (@) sin@) — sin), = 6sin (6) cos (6) + — sin (B) 08 (G) — = [vers Joo