《化学反应工程》(第五版)第二、第三章部分课后习题答案

C4H8C4H6+H24848484624646()()()()()()()()()ACHCHBCHCHHCCHCH+⇔⇔+⇔[phone]丁烯制丁二烯　假设反应按如下步骤进行::::（1111）分别写出AAAA、CCCC为控制步骤的均匀吸附动力学方程；（2222）写出BBBB为控制步骤的均匀吸附动力学方程，若反应物和产物的吸附都很弱，问，此时反应对丁烯是几级反应。48484848484848484848484848484644848464484846448484644848484848484848484848484846448464484644846448484848464622464622464622464622111166661111666648484848(1)1(1)1(1)1(1)111/1)211/1)211/1)211/1)233331111=4;=4;=4;=4;CHCHCHCHCHCHCHCHnnnnCHaCHidCHCHaCHidCHCHaCHidCHCHaCHidCHiiiinnnniCHCHCHCHiCHCHCHCHiCHCHCHCHiCHCHCHCHiiiiCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHHHCHCHHHCHCHHHCHCHHHPPPPrkpkrkpkrkpkrkpkbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpCHCHCHCHpppPpppPpppPpppPKKKKθθθθθθθθθθθθθθθθ====∗∗∗∗∗∗∗∗====∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗−−−−−−−−−−−−−−−−−−−−−−−−−=++−−−−−=++−−−−−=++−−−−−=++−−−−−−−−−−−−−−−−−−−−=−−−−=−−−−=−−−−=−−−−∑∑∑∑∑∑∑∑＝（，＝＋＋反应属于化学吸附控制，根据平衡近似假设：，由4式，又由表面反应的化学平衡：46246246246246246246246248484848484848484848484848462484624846248462484848484846246464846246464846246464846246465555////1/1/1/1/CHHCHHCHHCHHCHHCHHCHHCHHCHCHCHCHCHPCHPCHPCHPaaaaCHaCHaCHaCHaddddCHCHHpCHCHHpCHCHHpCHCHHpCHCHCHCHCHCHHpCHCHCHCHHpCHCHCHCHHpCHCHCHCHHpCHCHppPPppPPppPPppPPPPPPPKPKPKPKkkkkbkkbkkbkkbkkkkkkkpppKkpppKkpppKkpppKrrrrbppKbpbppKbpbppKbpbppKbp∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗=⇒=−=⇒=−=⇒=−=⇒=−========将上2、3、4、5条件代入1式，又有，并令，可得：（－）＝＋（）＋（（（（1111））））AAAA为控制步骤为控制步骤为控制步骤为控制步骤464646464646464646464646464646464646464648484644648484644648484644648484644648464648464648464648464648484848484822484822484822484822444411116666111146464646(1)1(1)1(1)1(1)111/1)2311/1)2311/1)2311/1)231111=4;=4;=4;=4;CHCHCHCHCHCHCHCHnnnnCHdCHaCHiCHdCHaCHiCHdCHaCHiCHdCHaCHiiiiinnnnCHCHCHCHiCHCHCHCHCHiCHCHCHCHCHiCHCHCHCHCHiCHCHCHCHCHiiiiCHCHCHCHCHCHCHCHCHCHCHCHCHCHHHCHCHHHCHCHHHCHCHHHCHCHCHCHPPPPrkkprkkprkkprkkpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpbpCHCHCHCHpppPpppPpppPpppPppppKKKKθθθθθθθθθθθθθθθθ====∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗====∗∗∗∗∗∗∗∗−−−−−−−−−−−−−−−−−−−−−=++−−−=++−−−=++−−−=++−−=−−−−=−−−−=−−−−=−−−−====∑∑∑∑∑∑∑∑＝（，＝＋＋由题设知反应属于的脱附控制，根据平衡近似假设：，由4式，又由表面反应的化学平衡：4848484822224646464648248248248246464646482464824648246482464646464646482484846482484846482484846482484866665555////1/1/1/1/PCHPCHPCHPCHHHHHCHCHCHCHCHHCHHCHHCHHaaaaCHaCHaCHaCHaddddCHpHCHCHpHCHCHpHCHCHpHCHCHCHCHCHCHCHpHCHCHCHCHpHCHCHCHCHpHCHCHCHCHpHCHCHKPKPKPKPppppPPPPPPPPPPPPkkkkbkkbkkbkkbkkkkkkkpKppkpKppkpKppkpKpprrrrbpKpbpbpKpbpbpKpbpbpKpbp∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗⇒=−⇒=−⇒=−⇒=−========将2、3、4、5代入1式，又有，并令，可得：（－）＝＋（）＋（（（（1111））））CCCC为控制步骤为控制步骤为控制步骤为控制步骤4848484848484848484848484846464846464846464846464848484822221111CHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHbpbpbpbpbpbpbpbpbpbpbpbpθθθθ∗∗∗∗∗∗∗∗∗∗∗∗−−−−−−−−−−−−−−−−由＝＋＋4848462484846248484624848462'1'1'1'1CHCHCHHCHCHCHHCHCHCHHCHCHCHHrkkPrkkPrkkPrkkPθθθθθθθθ=−−−=−−−=−−−=−−−4646484822464648482246464848224646484822,=3;,=3;,=3;,=3;CHCHCHCHHHCHCHCHCHHHCHCHCHCHHHCHCHCHCHHHpppppPpppppPpppppPpppppP∗∗∗∗∗∗∗∗∗∗∗∗==−−−−==−−−−==−−−−==−−−−反应属于化学反应控制，根据平衡近似假设：，48462484624846248462484646484646484646484646484648464846484648464846484648461212121212121212',',',',1111CHCHHCHCHHCHCHHCHCHHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHkpkppkpkppkpkppkpkppkkbkkbrkkbkkbrkkbkkbrkkbkkbrbpbpbpbpbpbpbpbp−−−−====++++++++令＝，＝4846484648464846484624846248462484624646464648464846484648464846484648464846''''1111CHCHHCHCHHCHCHHCHCHHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHkbpkbppkbpkbppkbpkbppkbpkbpprrrrbpbpbpbpbpbpbpbp−−−−====++++++++将上2、3代入1式，可得：（（（（2222））））BBBB为控制步骤为控制步骤为控制步骤为控制步骤48484848484848484848484848464648464648464648464648484848484846464848464648484646484846464848484848484848484848484846464846464846464846464848484848464648464648464648464648484848484484484484484648464846484611111111,2;,2;,2;,2;11111,11,11,11,1CHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCHCCHCCHCCHCbpbpbpbpbpbpbpbpbpbpbpbpppppppppppppppppbpbpbpbpbpbpbpbpbpbpbpbpCHCHCHCHCHCHCHCHbpbpbpbpbpbpbpbpbbbbθθθθθθθθθθθθ∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗∗−−−−−−−−==−−==−−==−−==−−≈≈≈≈＝＋＋由题设知反应属于化学反应控制，根据平衡近似假设：＝＋＋因为反应物，产物吸附都很弱，即：所以，888848484848CHCHCHCHHHHHpppp所以反应对与丁烯，是1级反应。（（（（2222）丁烯反应级数判断）丁烯反应级数判断）丁烯反应级数判断）丁烯反应级数判断2-102-102-102-10某氨合成催化剂还原后比表面积SSSSgggg=13.1=13.1=13.1=13.1mmmm2222/g/g/g/g，孔容VVVVgggg====0.082mL/g0.082mL/g0.082mL/g0.082mL/g。气体混合物中yyyyNH3NH3NH3NH3=0.09=0.09=0.09=0.09，yyyyH2H2H2H2=0.57=0.57=0.57=0.57，yyyyN2N2N2N2=0.19=0.19=0.19=0.19，yyyyCH4CH4CH4CH4=0.10=0.10=0.10=0.10，yyyyArArArAr=0.05=0.05=0.05=0.05，温度400400400400℃，压力30.4MPa30.4MPa30.4MPa30.4MPa。催化剂的孔隙率θ=0.50=0.50=0.50=0.50，曲折因子δ=2.5=2.5=2.5=2.5。已知计算分子扩散系数时，各组分的分子扩散体积如下：氢6.126.126.126.12；氮18.518.518.518.5；氨20.720.720.720.7；甲烷25.1425.1425.1425.14；氩16.216.216.216.2。求：(1)(1)(1)(1)计入KnudsenKnudsenKnudsenKnudsen扩散时，氨的有效扩散系数DDDDeffeffeffeff,NH3,NH3,NH3,NH3;;;;(2)(2)(2)(2)不计入KnudsenKnudsenKnudsenKnudsen扩散时，氨的有效扩散系数DDDDeffeffeffeff,NH3,NH3,NH3,NH3;;;;解：17171717;;;;40404040;;;;16161616;;;;2222;;;;28282828;;;;7777....20202020))))((((;;;;2222....16161616))))((((;;;;14141414....2525