4.1-4.3热力学参数
热力学第二定律

二. 熵(entropy)S
dQ T 0 R
1 R2 R1
2
存在一个与过程 无关的状态量
( 2)
p
d Q (1) d Q T T 0 (1) ( 2)
R1 R2
0
( 2)
V
d Q ( 2) d Q ( 2) d Q 令 S2 S1 S T T T (1) (1) (1) R1 R2 R —任意可逆过程 熵增(量)
10
二 . 不可逆过程是相互沟通的 热二律的 开氏表述
功全部转换成热而不产生其 它影响的过程是不可逆的
(否则热全部转换为功而不产生其它影响成立, 这就违背了热二律的开氏说法。) 热二律的 克氏说法 有限温差热传导不可逆
开氏、克氏 表述的等价
功、热转换 的不可逆性
热传导的 不可逆性
11
实际上,一切不可逆过程都是相互沟通的。 例如: 功变热而不产生其他影 响之不可逆(开氏表述) 可导出 证明: T
25
SCu
Q吸 mc(T1 T2 ) 水恒温吸热:S水 0 T2 T2 T1 T1 S总 S水 SCu mc( 1 ln ) 0(自己证) T2 T2
dT T2 mc mc ln 0 T T1 T1
T2
[例2] 已知: 1mol理气经绝热自由膨胀体积加倍
气体
气体自由膨 胀之不可逆
T
Q T
绝热壁
A=Q 等 价
Q
气体
A=Q
设气体能 气体 T 自动收缩 导致
循环,无变化
不成立 不成立 任何一种不可逆过程的表述,都可作为热力学第 二定律的表述! 12
§4.4 卡诺定理(Carnot theorem)
热力学基本关系式

)S
(V S
)
p
(Sp)T (VT)p
第17页,本讲稿共62页
4.7热力学关系式的应用
18
4.7.1材料热力学中一些常见的定义公式
U T
V
CV
H T
P
CP
CI
T S T I
S C p T p T
S CV T V T
恒压膨胀 V 系 V 1数 V TP
恒容压力 系 1数 P
U T p p V T T V
对理想气体而言:
U VT
Tp TV
pTTnVRTV
p
TnRppp0 V
由U=U(T,V),已证明理想气体的热力学能在定温下与 体积无关,所以U只是温度的函数。
第27页,本讲稿共62页
28
4.7.6理想气体的内能和焓
同理:
H p
T
T V T
p
V
对应系数关系式讲的是特性函数与其某一特征变
量的偏微商关系,脚标为该特性函数的另一特征变量 ,结果等于偏微特征变量的共轭变量。
U H T S V S p
U F p V S V T
H p
S
G p
T
V
F G S T V T p
第16页,本讲稿共62页
dG -SdT VdP
G S T P
G V P T
H G TS G T G T P
U H - PV G - T G P G T P P T
F G PV G P G P T
常用的特性函数与特征变量为:
G(T ,P ) F(T ,V ) U( S ,V )
和教材 P52的推导 进行比较
H p T G p T T T 2 G p V T T G p T p V T V T p
化工热力学Ⅱ(高等化工热力学)——第四章 混合物的逸度.

4.1逸度及逸度系数 定义 dμi= d Gi =RTdlnfi
(1-49)
lim fi
p0
yiP
=1
逸度系数: i fi / yiP
(1-50)
4.1.1 以P.T为独立变量
由定义,有dGi =RTdlnf=i RTln(ipyi) =RT(dln i+dlnP) (恒温恒组成) (1)
由热力学函数:dGi=-Sdi T+Vi dP= VidP
(恒T)
(2)
由式(1) (2) 联立,得 d lnˆi
积分得:lnˆi
p 0
(
Zi
-1)
dP P
Vi dP d ln P RT
(恒温恒组成)
(4-1)
或
ln ˆi =
1 RT
p
0
(Vi-RPT)dP
4.1.2 以 V, T为独立变量
ˆi= 2
lnˆi= Vm0p
k
y j1
(Z-1)
jB
dP P
j-lnZ (4-6) (4-1)
式中:Z=PVm/RT=1+B’P=1+BP/RT
Z= i
(nZ) n
i
T,P,n
j
=
(n+nBP/RT) n
i
T,P,n
j
=1+
P RT
=y1B11+y2B22+y1y2(2B12-B11-B22)
=y1B11+y2B22+y1y2δ12 式中δ12=2B12-B11-B22
nB=n1B11+n2B22+(n1n2/n)δ12 上式对n1求偏导,得:
第四章热力学参数状态图详解

相连,所连直线与 G=A+BT/K线相交,交点温度即为还原温度。
(3)在给定温度及CO/CO2比值条件下,判断气氛对金属的性质 方法是:先求出指定温度下的平衡CO/CO2比,然后将指定的CO/CO2 比值与CO/CO2的平衡值相比较,若前者大于后者,则气氛对金属讲是还 原性的,即发生金属氧化物被CO还原的反应,反之发生金属被CO2氧化的 反应。
4.2 理查森(Richardson)-杰弗斯(Jeffes)图
1. 自由能标尺: (1)直线的斜率
表明图中直线的斜率即为氧化物的 标准熵变。当反应物质发生相变时,直 线斜率也发生变化,表现在直线中出现 拐点。 (2)直线的位置
不同元素的氧化物标准吉布斯自由 能变化与T的关系构成位置高低不同的 直线,由此可得出:
碳热还原法是利用碳还原金属氧化物制取纯 金属的一种方法。在工艺过程中,金属易与 碳生成碳化物,且在一定范围内,生成的CO 可 按 布 氏 ( Boudouard ) 反 应 进 行 分 解 , 即 2CO = C(S) +CO2,从而使还原反应变得复杂 化。若将各还原反应的反应吉布斯自由能的 变化对T的关系绘制成图,则可直观地看出还 原反应的顺序,并可以从图上直接读出各反 应进行的温度及压力条件。
E—pH图分析 (1) 水的稳定性
右图为 Fe—H2O系E—pH图,图中,a线以下, 电位比氢的电位值负,发生H2的析出,表明水不稳 定。a线以上,电位比H2的电位正,发生氢的氧化, 水是稳定的。同理b线以上析出O2,水不稳定,b线 以下,氧还原为OH-,水是稳定的。 (2) 图中点、线、面的意义
热力学参数

q 622e p 0.378e
式中 p , e 仍以 hPa 为单位。
(4.1.7)
8.饱和比湿 qs 饱和湿空气中含有的水汽与湿空气质量之比。
qs 0.622es 克 / 克 p 0.378es
622es 克 / 千克 p 0.378es
0.622 e 克 / 克 Pe
622
P
e
克 e
/
千克
(4.1.9)
M v , M d 分别为湿空气中的水汽和干空气的质量 v , d 分别为水汽和干空气的的密度 P 为气压, e 为水汽压,均以 hPa 为单位。
10.相对湿度 RH 实际水汽压与同温下饱和水汽压之比。
RH e 100% es
一般情况下,
q
4
102
克/克,所以
R Cp
的值总在
0.288
和 0.285 之间变化,变化范围很小,日常计算中选取
R 0.286 较为适合,因此
Cp
T
P0
0.286
P
上式是常用的位温计算公式。
(4.3.2)
位温是一个重要的温度参量,在干绝热过程中位温 是守恒的。
可以用它来比较不同气压情况下空气质块的热力 差异,来分析大气的稳定度状况;
常用的参量有:
露点 Td , 温度露点差 T Td ,
水气压 e ,
绝对湿度 a (也称为水汽密度 v ),
比湿 q , 混合比 W , 相对温度 RH 饱和差 d 等等
1.露点(或称露点温度) Td 空气在定压冷却过程中,发生凝结现象时的温度。
这在日常工作中最容易从地面天气报告、气压表、高空 压温湿记录月报表等资料来源中获得的温度特征参量。
热力学参数表

Standard Thermodynamic ValuesFormula State of Matter Enthalpy(kJ/mol)Entropy (Jmol/K)Gibbs Free Energy(kJ/mol)(NH4)2O (l) -430.70096267.52496 -267.10656 (NH4)2SiF6 (shexagonal) -2681.69296280.24432 -2365.54992 (NH4)2SO4 (s) -1180.85032220.0784 -901.90304 Ag (s) 042.55128 0 Ag (g) 284.55384172.887064245.68448 Ag+1 (aq) 105.57905672.67608 77.123672 Ag2 (g) 409.99016257.02312 358.778 Ag2C2O4 (s) -673.2056209.2 -584.0864 Ag2CO3 (s) -505.8456167.36 -436.8096 Ag2CrO4 (s) -731.73976217.568 -641.8256 Ag2MoO4 (s) -840.5656213.384 -748.0992 Ag2O (s) -31.04528121.336 -11.21312 Ag2O2 (s) -24.2672117.152 27.6144 Ag2O3 (s) 33.8904100.416 121.336 Ag2S (sbeta) -29.41352150.624 -39.45512 Ag2S (s alpha orthorhombic) -32.59336144.01328 -40.66848 Ag2Se (s) -37.656150.70768 -44.3504 Ag2SeO3 (s) -365.2632230.12 -304.1768 Ag2SeO4 (s) -420.492248.5296 -334.3016 Ag2SO3 (s) -490.7832158.1552 -411.2872 Ag2SO4 (s) -715.8824200.4136 -618.47888 Ag2Te (s) -37.2376154.808 43.0952 AgBr (s) -100.37416107.1104 -96.90144 AgBrO3 (s) -27.196152.716 54.392 AgCl (s) -127.0680896.232-109.804896 AgClO2 (s) 8.7864134.55744 75.7304 AgCN (s) 146.0216107.19408 156.9 AgF•2H2O (s) -800.8176174.8912 -671.1136 AgI (s) -61.83952115.4784-66.19088 AgIO3 (s) -171.1256149.3688 -93.7216 AgN3 (s) 308.7792104.1816 376.1416 AgNO2 (s) -45.06168128.19776 19.07904 AgNO3 (s) -124.39032140.91712 -33.472 AgO (s) -11.4223257.78104 14.2256 AgOCN (s) -95.3952121.336 -58.1576 AgReO4 (s) -736.384153.1344 -635.5496 AgSCN (s) 87.864130.9592 101.37832 Al (s) 028.32568 0 Al (l) 8.6608835.229286.61072 Al (g) 326.352164.4312285.7672 Al(BH4)3 (l) -16.3176289.1144 144.7664 Al(BH4)3 (g) 12.552379.0704 146.44 Al(CH3)3 (l) -136.3984209.4092 -10.0416Al(NO3)3•6H2O (s) -2850.47552467.7712 -2203.88016 Al(NO3)3•9H2O (s) -3757.06464569.024 -2929.6368 Al(OH)3 (s) -1284.48871.128 -1305.8264 Al+3 (aq) -531.368-321.7496 -485.344 Al2(CH3)6 (g) -230.91496524.6736 -9.79056 Al2(SO4)3 (s) -3435.064239.3248 -3506.6104 Al2Br6 (g) -1020.896547.2672 -947.2576 Al2Cl6 (g) -1295.3664475.5116 -1220.8912 Al2F6 (g) -2631.736387.02 -2539.688 Al2I6 (g) -506.264584.0864 -560.656 Al2O (g) -131.3776259.408 -161.084 Al2O3 (l) -1581.133689.57944-1499.25272-1656.86459.8312 -1562.724 gamma-corundum)Al2O3 (salpha-corundum)-1675.273650.91928 -1581.9704 Al2O3 (sgibbsite) -2562.7140.20584 -2287.3928 Al2O3•3H2O (sboehmite) -1974.84896.8596 -1825.4792 Al2O3•H2O (sAl2O3•H2O (sdiaspore) -1999.95270.54224 -1840.96halloysite) -4079.8184203.3424 -3759.324 Al2Si2O7•2H2O (skaolinite) -4098.6464202.924 -3778.152 Al2Si2O7•2H2O (sandalusite) -2591.98893.3032 -2444.7112 Al2SiO5 (skyanite) -2596.17283.80552 -2443.8744 Al2SiO5 (ssillimanite) -2593.243296.19016 -2442.6192 Al2SiO5 (sAl4C3 (s) -207.27536104.6 -238.44616 Al4C3 (g) -215.894489.1192 -203.3424 Al6BeO10 (l) -5299.4544314.88784 -5034.1888 Al6BeO10 (s) -5624.1328175.56064 -5317.4456 mullite) -6819.92274.8888 -6443.36 Al6Si2O13 (sAlBO2 (g) -541.4096269.4496 -550.6144 AlBr3 (s) -511.11744180.24672 -488.31464 AlBr3 (l) -501.20136206.4804 -486.26448 AlBr3 (g) -410.8688349.07112 -438.4832 AlC (g) 689.5232223.34192 633.0392 AlCl (g) -51.4632227.86064 -77.8224 AlCl2 (g) -288.696288.2776 -299.5744 AlCl3 (g) -584.5048314.30208 -570.07 AlCl3 (s) -705.6316109.28608 -630.06856 AlCl3 (l) -674.79552172.92472 -618.186 AlCl3•6H2O (s) -2691.5672376.56 -2269.4016 AlF (g) -265.2656215.0576 -290.788 AlF2 (g) -732.2263.1736 -740.568 AlF3 (s) -1510.42466.48376 -1430.928-1192.8584 AlF3 (g) -1209.176276.7716AlF3•3H2O (s) -2297.4344209.2 -2051.8336 AlH (g) 259.24064187.77792 231.166 AlI3 (l) -297.064219.66 -301.248 AlI3 (g) -205.016363.1712 -251.04AlI3 (s) -309.616189.5352 -305.432-287.0224 AlN (s) -317.98420.16688AlN (g) 435.136211.7104 410.032 AlO (g) 83.68218.27928 57.7392 AlOCl (s) -793.286454.392 -737.26264 AlOCl (g) -348.1088248.82248 -350.2008 AlOF (g) -586.5968234.26216 -587.0152 AlOH (g) -179.912216.3128 -184.096 AlPO4 (sberlinite) -1692.009690.7928 -1601.2168 AlS (g) 200.832230.49656 150.2056 Ar (g) 0154.732688 0 Au (g) 366.1180.39316 326.352 Au (s) 047.40472 0 Au(CN)2-1 (aq) 242.2536171.544 285.7672 AuBr4-1 (aq) -191.6272335.9752 -167.36 AuCl4-1 (aq) -322.168266.9392 -237.31648 AuH (g) 294.972211.045144 265.684518.816 B (g) 562.748153.3436B (s) 0 5.8576 0 B(CH3)3 (l) -143.0928238.9064 -32.2168 B(CH3)3 (g) -124.2648314.6368 -35.9824 B(OH)4-1 (aq) -1344.02632102.508 -1153.3196 B2 (g) 830.524201.79432 774.04 B2Cl4 (l) -523262.3368 -464.8424 B2H6 (g) 35.564232.0028 86.6088 B2O2 (g) -454.8008242.37912 -462.332 B2O3 (g) -843.78728279.7004 -831.9884 amorphous) -1254.5305677.8224 -1182.3984 B2O3 (sB2O3 (s) -1272.772853.9736 -1193.6952 B3N3H6 (l) -540.9912199.5768 -392.79392 B4C (s) -71.12827.11232 -71.128 B5H9 (l) 42.6768184.22152 171.66952 Ba (s) 062.3416 0146.8584 Ba (g) 179.0752169.99592Ba (l) 4.9789666.7348 3.84928 Ba(BrO3)2 (s) -752.65976242.672 -577.392 Ba(BrO3)2•H2O (s) -1054.7864292.4616 -824.62456 Ba(ClO3)2 (s) -680.3184196.648 -531.368 Ba(ClO4)2•3H2O (s) -1691.5912393.296 -1270.6808 Ba(IO3)2 (s) -1027.172249.3664 -864.8328 Ba(IO3)2•H2O (s) -1322.144297.064 -1104.1576 Ba(N3)2•H2O (s) -308.3608188.28 -105.0184 Ba(NO3)2 (s) -992.06824213.8024 -796.71728 Ba(OH)2•8H2O (s) -3342.1792426.768 -2793.2384 Ba(ReO4)2•4H2O (s) -3368.12376.56 -2918.34 Ba+2 (aq) -537.6449.6232 -560.73968Ba2TiO4 (s) -2243.0424196.648 -2133.0032BaBr2 (s) -757.304146.44 -736.8024BaBr2 (g) -439.32330.536 -472.792BaBr2•2H2O (s) -1366.076225.936 -1230.5144BaCl2 (s) -858.1384123.67904 -810.4408BaCl2 (l) -832.44864143.5112 -790.1484BaCl2 (g) -498.7328325.64072 -510.69904BaCl2•2H2O (s) -1460.13232202.924 -1296.45424witherite) -1216.2888112.1312 -1137.6296 BaCO3 (sBaCrO4 (s) -1445.9904158.5736 -1345.28152BaF2 (s) -1208.757696.39936 -1158.5496-1128.38296 BaF2 (l) -1171.3108121.25232BaF2 (g) -803.7464301.16432 -814.49928-353.42248 BaI2 (g) -302.9216348.1088-587.39176 BaI2 (l) -585.88552183.6776-601.40816 BaI2 (s) -605.4248165.14248 BaMoO4 (s) -1548.08138.072 -1439.7144-520.40592 BaO (s) -548.10472.09032-471.24392 BaO (l) -491.6296.56672-144.80824 BaO (g) -123.8464235.35BaS (s) -460.2478.2408 -456.056BaSeO3 (s) -1040.5608167.36 -968.1776BaSeO4 (s) -1146.416175.728 -1044.7448BaSiF6 (s) -2952.2304163.176 -2794.0752BaSiO3 (s) -1623.6012109.6208 -1540.25592BaSO4 (s) -1473.1864132.2144 -1362.3104BaTiO3 (s) -1659.7928107.9472 -1572.3472BaZrO3 (s) -1779.4552124.6832 -1694.52BBr (g) 238.0696224.89 195.3928-232.46304 BBr3 (g) -205.6436324.13448BBr3 (l) -239.7432229.7016 -238.488BCl (g) 149.49432213.13296 120.9176BCl2F (g) -645.1728284.512 -631.3656-388.73544 BCl3 (g) -403.756289.99304BCl3 (l) -427.1864206.2712 -387.4384BClF2 (g) -890.3552271.96 -876.1296Be (g) 324.26136.1892 286.604Be (l) 12.0499216.5268 9.95792Be (s) 09.53952 0beta) -905.83646.024 -816.7168 Be(OH)2 (sBe+2 (aq) -382.836-129.704 -379.698Be2C (s) -117.15216.3176 -87.864Be2SiO4 (s) -2149.320864.30808 -2032.5872Be3N2 (scubic) -588.270434.14144 -533.0416BeAl2O4 (s) -2300.781666.27456 -2178.6088BeBr2 (s) -369.8656106.2736 -353.1296BeC2 (g) 564.84218.4048 506.264 beta) -496.222475.81408 -449.52896 BeCl2 (salpha) -1026.753653.346 -979.4744 BeF2 (aBeH (g) 326.7704170.87456 298.3192 BeI2 (s) -192.464120.4992 -209.2 alpha) -608.353613.76536 -579.0656 BeO (sBeO (g) 129.704197.52664 104.1816 BeO2-2 (aq) -790.776158.992 -640.152 alpha) -1205.201277.98976 -1093.86496 BeSO4 (sBeSO4•4H2O (s) -2423.74936232.96512 -2080.66136 BeWO4 (s) -1514.60888.36608 -1405.824-149.7872 BF (g) -122.1728200.37176-1120.34968 BF3 (g) -1137.002254.01064BF4-1 (aq) -1574.8576179.912 -1486.9936 BH (g) 449.61264171.7532419.61336 BH4-1 (aq) 48.15784110.4576 114.26504614.50408 BN (g) 647.474212.17064-228.4464 BN (s) -254.387214.81136BO (g) 25.104203.42608 -4.184 BO2 (g) -300.4112229.45056 -305.8504 BO2-1 (aq) -772.3664-37.2376 -678.9376882.428984 Br (g) 111.884344174.91212Br-1 (aq) -121.545282.4248 -103.9724 Br2 (l) 0152.230656 0 Br2 (g) 30.907208245.353944 3.142184 Br2Cl-1 (aq) -170.2888188.6984 -128.4488 Br3-1 (aq) -130.41528215.476 -107.06856 BrCl (g) 14.644239.99424 -0.96232-109.16056 BrF (g) -93.84712228.8648BrF3 (l) -300.8296178.2384 -240.58 BrF3 (g) -255.60056292.41976-229.45056 BrF5 (l) -458.5664225.0992 -351.8744108.24008 BrO (g) 125.77104237.442BrO-1 (aq) -94.1441.84 -33.472 BrO3-1 (aq) -83.68163.176 1.6736671.289328C (g) 716.681544157.98658482.899512diamond) 1.8966072 2.376512C (sgraphite) 0 5.694424 0 C (sC-1 (g) 587.852151.29344 550.6144 C12H22O11 (s) -2225.4696360.2424 -1544.64912781.5712 C2 (g) 837.6368199.28392C2-1 (g) 443.504196.48064 393.296754.3752 C3 (g) 820.064237.2328cyclopropane) 53.30416237.442 104.3908 C3H6 (gC3O2 (l) -117.27752181.08352 -105.0184 C3O2 (g) -93.7216276.3532 -109.83C4H10CH3(CH2)2CH(g n-butane) -126.1476310.11808 -17.1544 3cyclobutane) 26.65208265.39112 110.0392 C4H8 (gC4N2 (g) 533.46289.99304 510.8664cyclopentane) -77.23664292.88 38.61832 C5H10 (gcyclopentane) -105.77152204.26288 36.4008 C5H10 (lcyclohexane) -123.13512298.23552 31.75656 C6H12 (gcyclohexane) -156.23056204.34656 26.65208 C6H12 (ltoluene) 12.00808220.95704 113.76296 C6H5CH3 (ltoluene) 49.9988320.66176 122.00544 C6H5CH3 (gC6H5COOH (s benzoic acid) -385.05352167.5692 -245.26608phenol) -96.35752315.59912 -32.88624 C6H5OH (gphenol) -165.01696144.01328 -50.4172 C6H5OH (sC6H6 (lbenzene) 48.99464173.25944 124.34848benzene) 82.92688269.19856 129.66216 C6H6 (gC7H14 (lcycloheptane) -156.77448242.54648 54.05728cyclooctane) -169.78672262.00208 77.8224 C8H16 (lCa (s) 041.4216 0Ca (l) 10.9202450.66824 8.20064145.51952 Ca (g) 179.2844154.76616Ca(ClO4)2•4H2O (s) -1948.9072433.4624 -1476.82648Ca(H2PO4)2•H2O (s) -3409.66712259.8264 -3058.42032Ca(IO3)2 (s) -1002.4864230.12 -839.3104Ca(IO3)2•6H2O (s) -2780.6864451.872 -2267.728Ca(NO3)2 (s) -938.38752193.3008 -743.20392Ca(NO3)2•2H2O (s) -1540.758269.4496 -1229.34288Ca(NO3)2•3H2O (s) -1838.0312319.2392 -1471.9312Ca(NO3)2•4H2O (s) -2132.33376375.3048 -1713.47352Ca(OH)2 (s) -986.168883.38712 -898.514dolomite) -2326.304155.18456 -2163.5464 Ca[Mg(CO3)2] (sCa+1 (g) 775.2952160.535896 733.4552Ca+2 (aq) -542.83216-53.1368 -553.5432hydroxyapatite) -13476.664780.7344 -12677.52 Ca10(PO4)6(OH)2 (sfluorapatite) -13744.44775.7136 -12982.952 Ca10(PO4)6F2 (sbeta) -3338.832189.24232 -3132.1424 Ca2P2O7 (sbeta) -2307.476127.73752 -2192.8344 Ca2SiO4 (sgamma) -2317.936120.79208 -2201.2024 Ca2SiO4 (sCa3(AsO4)2 (s) -3298.6656225.936 -3063.1064beta) -4120.8216235.9776 -3884.844 Ca3(PO4)2 (sCa3(PO4)2 (salpha) -4109.9432240.91472 -3875.6392CaBr2 (g) -384.928314.6368 -420.95224CaBr2 (s) -683.2472129.704 -664.12632CaBr2 (l) -662.99664147.86256 -649.31496CaBr2•6H2O (s) -2506.216410.032 -2153.0864CaC2 (s) -59.831269.95648 -64.852CaC2O4•H2O (s) -1674.8552156.4816 -1513.9804CaCl2 (s) -795.7968104.6 -748.0992CaCl2 (l) -774.04123.8464 -732.2CaCl2 (g) -471.5368289.9512 -479.068aragonite) -1207.1258488.7008 -1127.7972 CaCO3 (scalcite) -1206.9166492.8848 -1128.8432 CaCO3 (sCaCrO4 (s) -1379.0464133.888 -1277.3752CaF2 (g) -782.408273.6336 -794.96CaF2 (s) -1219.63668.86864 -1167.336CaF2 (l) -1184.07292.59192 -1142.232CaH2 (s) -186.18841.84 -147.2768CaHPO4 (s) -1814.3916111.37808 -1681.25672CaHPO4•2H2O (s) -2403.58248189.45152 -2154.76CaI2 (l) -500.15536178.94968-506.51504-533.12528 CaI2 (s) -536.8072145.26848CaI2 (g) -258.1528327.43984 -308.7792CaMoO4 (s) -1541.3856122.5912 -1434.6936CaO (s) -635.131238.19992 -603.542CaO (l) -557.3506462.29976-532.95792CaO•2Al2O3 (s) -3977.7288177.82 -3770.6208CaO•2B2O3 (s) -3360.25408134.7248 -3167.12064CaO•Al2O3 (s) -2326.304114.2232 -2208.7336CaO•B2O3 (s) -2030.95544104.85104 -1924.09608CaO•Fe2O3 (s) -1520.34008145.35216 -1412.81128diopside) -3206.1992142.92544 -3032.1448 CaO•MgO•2SiO2 (sCaO•V2O5 (s) -2329.27464179.0752 -2169.69688CaS (s) -474.88456.484 -469.8632CaSe (s) -368.19266.944 -363.1712CaSeO4•2H2O (s) -1706.6536221.752 -1486.9936pseudowollastonite)-1628.412887.36192 -1544.7328 CaSiO3 (swollastonite) -1634.9398481.92272 -1549.71176 CaSiO3 (sCaSO3•H2O (s) -1752.6776184.096 -1555.1928CaSO4 (s anhydrite insoluble) -1434.10784106.692 -1321.85112CaSO4 (s alpha soluble) -1425.23776108.3656 -1313.48312CaSO4 (s beta soluble) -1420.80272108.3656 -1309.04808CaSO4•0.5H2O (s beta micro) -1574.6484134.3064 -1435.86512CaSO4•0.5H2O (s alpha macro) -1576.7404130.5408 -1436.82744CaSO4•2H2O (s) -2022.62928194.1376 -1797.4464perovskite) -1660.629693.63792 -1575.276 CaTiO3 (ssphene) -2603.2848129.20192 -2461.8656 CaTiSiO5 (sCaWO4 (s) -1645.1488126.39864 -1538.49864CaZrO3 (s) -1766.9032100.08128 -1681.1312CBr (g) 510.448233.4672 464.424CCl (g) 502.08224.30424 468.60877.44584 Cd (g) 112.00568167.636144gamma) 051.75608 0 Cd (salpha) -0.5857651.75608 -0.58576 Cd (sCd(CN)4-2 (aq) 428.0232322.168 507.5192 Cd(NH3)4+2 (aq) -450.1984336.3936 -226.3544 CdBr2 (s) -316.18488137.2352 -296.31088 CdBr2•4H2O (s) -1492.55832316.3104 -1248.032808 CdCl2 (s) -391.49688115.2692 -343.96664 CdCl2•2.5H2O (s) -1131.93936227.1912 -944.094496 CdCl3-1 (aq) -561.0744202.924 -487.0176 CdCO3 (s) -750.609692.4664 -669.44 CdF2 (s) -700.401677.404 -647.6832-201.37592 CdI2 (s) -202.924161.084CdI4-2 (aq) -341.8328326.352 -315.892 CdO (s) -258.152854.8104 -228.4464 CdS (s) -161.920864.852 -156.4816 CdSb (s) -14.3929692.8848 -13.01224 CdSeO3 (s) -575.3142.256 -497.896 CdSeO4 (s) -633.0392164.4312 -531.7864 CdSiO3 (s) -1189.092897.4872 -1105.4128 CdSO4 (s) -933.28304123.038888 -822.7836 CdSO4•8/3H2O (s) -1729.37272229.630472 -1465.337216 CdSO4•H2O (s) -1239.55184154.029776 -1068.84464 CdTe (s) -92.4664100.416 -92.048 CF (g) 255.224212.92376 221.752 CF+1 (g) 1149.3448201.2504 1115.036 CF2 (g) -182.004240.70552 -191.6272 CF2+1 (g) 941.8184246.6468 924.2456 CH3(CH2)2CH2OH (g 2-butanol) -274.6796362.7528 -150.79136 1-butanol) -327.10512226.3544-162.50656 CH3(CH2)2CH2OH (l-15.0624 n-butane) -147.65336230.9568CH3(CH2)2CH3 (lpentane) -146.44348.9456-8.368 CH3(CH2)3CH3 (ghexane) -167.19264388.40072 -0.25104 CH3(CH2)4CH3 (gCH3(CH2)4CH3 (l hexane) -198.82368296.05984 -3.80744 CH3(CH2)5CH3 (gheptane) -187.77792427.89768 7.99144heptane) -224.38792326.017281.75728 CH3(CH2)5CH3 (l7.40568octane) -249.95216357.732CH3(CH2)6CH3 (l16.40128 CH3(CH2)6CH3 (goctane) -208.44688466.7252nonane) -275.47456393.67256 11.75704 CH3(CH2)7CH3 (lnonane) -229.03216505.67824 24.81112 CH3(CH2)7CH3 (gCH3(CH2)8CH3 (l decane) -301.0388425.5128 -17.53096 1-propanol) -304.00944194.556 -170.62352 CH3CH2CH2OH (l1-propnaol) -256.39552324.72024 -161.79528 CH3CH2CH2OH (gpropane) -103.84688270.20272 -23.55592 CH3CH2CH3 (g2-butanol) -292.62896358.9872 -167.61104 CH3CH2CHOHCH3 (g-177.02504 2-butanol) -342.58592225.0992CH3CH2CHOHCH3 (ldiethyl ether) -273.2152253.132 -116.64992 CH3CH2OCH2CH3 (lCH3CH2OCH2CH3 (gdiethyl ether) -252.12784342.6696 -122.34016ethanol) -276.9808161.04216 -174.17992 CH3CH2OH (lCH3CH2OH (gethanol) -234.42952282.58736 -167.90392ethane) -84.68416229.11584 -32.80256 CH3CH3 (g2-propanol) -272.42024309.90888 -173.38496 CH3CHOHCH3 (g2-propanol) -317.85848180.58144 -180.28856 CH3CHOHCH3 (lacetone) -247.60912200.4136 -155.72848 CH3COCH3 (lacetone) -216.64752294.93016 -153.05072 CH3COCH3 (gCH3COOH (l acetic acid) -484.13064159.8288 -389.9488 CH3COOH (g acetic acid) -434.84312282.50368 -376.68552 CH3OCH3 (g dimethyl ether) -184.05416267.06472 -112.92616 methanol) -201.08304239.70136 -162.42288 CH3OH (gmethanol) -239.03192127.23544 -166.81608 CH3OH (lmethane) -74.85176186.27168 -50.8356 CH4 (g105.31128 Cl (g) 121.29416165.0588-131.25208 Cl-1 (aq) -167.150856.484Cl2 (g) 0222.96536 0 Cl2F6 (g) -339.3224489.528 -237.2328 Cl2O (g) 80.3328267.85968 97.4872 ClF (g) -54.47568217.7772-55.94008 ClF3 (g) -158.992281.49952 -118.8256 ClF3•HF (g) -450.6168359.824 -384.0912 ClF5 (g) -238.488310.62016 -146.44 ClO (g) 101.21096226.5636 97.4872 ClO-1 (aq) -107.110441.84 -36.8192 ClO2 (g) 102.508256.77208 120.33184 ClO2-1 (aq) -66.5256101.2528 17.1544 ClO3-1 (aq) -99.1608162.3392 -3.3472 ClO3F (g) -27.15416278.8636 44.85248 ClO4-1 (aq) -129.32744182.004 -8.61904 CN (g) 435.136202.54744 405.0112 CN+1 (g) 1802.8856213.34216 1763.1376 CN-1 (aq) 150.62494.14 172.3808 CN-1 (g) 60.668195.8112 38.74384 CN2 (g) 581.576231.5844 573.208 CNBr (g) 181.3764247.14888 160.62376 CNCl (g) 132.2144235.47552 125.47816196.14592 CNI (g) 225.0992256.60472169.36832 CNI (s) 160.2472128.8672hexagonal) 030.04112 0 Co (s-137.27704 CO (g) -110.54128197.9032Co (s face centered cubic) 0.4602430.71056 0.25104 Co(IO3)2•2H2O (s) -1081.9824267.776 -795.7968 Co(NH3)6+3 (aq) -584.9232146.44 -157.3184 pink) -539.73679.496 -454.3824 Co(OH)2 (sCo+2 (aq) -58.1576-112.968 -54.392 Co+3 (aq) 92.048-305.432 133.888-394.38384 CO2 (g) -393.5052213.67688CO2 (aq-386.01584 undissoc) -413.7976117.5704CO3-2 (aq) -677.13856-56.9024 -527.89528 Co3O4 (s) -910.02114.2232 -794.96 COBr2 (g) -96.232308.9884 -110.876 CoCl2 (s) -312.5448109.16056 -269.868 COCl2 (g) -220.9152283.75888 -206.77328 CoCl2•2H2O (s) -922.9904188.28 -764.8352 CoCl2•6H2O (s) -2115.4304343.088 -1725.4816 CoCl3 (g) -163.5944334.0924 -154.51512 CoF2 (s) -692.033681.96456 -647.2648 COF2 (g) -640.152258.73856 -624.58752 CoF3 (s) -790.77694.5584 -719.648 CoO (s) -237.9440852.96944 -214.2208-165.64456 COS (g) -138.40672231.45888CoSi (s) -100.41643.0952 -98.7424 CoSO4 (s) -888.2632117.9888 -782.408 CoSO4•6H2O (s) -2683.6176367.60624 -2235.7204 CoSO4•7H2O (s) -2979.92848406.0572 -2473.83184352.58568 Cr (g) 397.48174.2217622.34256 Cr (l) 26.10397636.23344Cr (s) 023.61868 0 Cr23C6 (s) -364.8448610.0272 -373.6312-102.21512 Cr2N (s) -125.5264.852Cr2O3 (s) -1134.700881.1696 -1053.1128 Cr2O3 (l) -1018.3856125.60368 -950.06088 Cr2O7-2 (aq) -1490.3408261.9184 -1301.224 Cr3C2 (s) -85.353685.43728 -86.31592 Cr7C3 (s) -161.9208200.832 -166.9416 CrCl2 (s) -395.388115.31104 -356.0584 CrCl3 (s) -556.472123.0096 -486.1808 CrF3 (s) -1158.96893.88896 -1087.84 CrN (g) 505.0088230.45472471.91336 CrN (s) -117.15237.69784 -92.80112 CrO (g) 188.28239.15744 154.5988 CrO2 (g) -75.312269.11488 -87.36192 CrO2Cl2 (l) -579.484221.752 -510.8664 CrO2Cl2 (g) -538.0624329.6992 -501.6616 CrO3 (g) -292.88266.06056 -273.46624 CrO4-2 (aq) -881.150450.208 -727.84864 Cs (g) 76.5672175.47696 49.78960.025104 Cs (l) 2.08781692.08984Cs (s) 085.1444 0 CS (g) 234.304210.4552 184.096 Cs+1 (aq) 458.5664169.72396 427.1864 CS2 (g) 117.06832237.77672 66.90216 CS2 (l) 89.70496151.33528 65.2704Cs2O (g) -92.048317.984 -104.6CsAl(SO4)2•12H2O (s) -6064.708686.176 -5098.204CsBr (s) -405.68064113.3864 -384.928CsCl (s) -442.83456101.181672 -414.216CsCl (l) -434.2992101.71304 -406.2664CsCl (g) -240.1616255.97712 -257.7344CsF (s) -554.798488.2824 -525.5104-515.09224 CsF (l) -543.8363290.08152CsF (g) -356.4768243.0904 -373.2128CsH (g) 121.336214.43 101.6712-333.71584 CsI (s) -336.812125.52CsOH (s) -416.726498.7424 -362.3344CsOH (g) -259.408255.14032 -259.8264CsOH (l) -406.01536118.44904 -365.8908298.61208 Cu (g) 338.31824166.27216Cu (s) 033.149832 0Cu(C2O4)2-2 (aq) -1592.012146.44 -1335.9512Cu(IO3)2•H2O (s) -692.0336247.2744 -468.608Cu(NH3)+2 (aq) -38.911212.1336 15.56448Cu(NH3)2+2 (aq) -142.256111.2944 -30.45952Cu(NH3)3+2 (aq) -245.6008199.5768 -73.13632Cu(NH3)4+2 (aq) -348.5272273.6336 -111.2944Cu(OH)2 (s) -450.1984108.3656 -372.7944Cu+1 (aq) 71.6719240.5848 49.9988Cu+2 (aq) 64.76832-99.5792 65.52144431.95616 Cu2 (g) 484.17248241.45864Cu2O (s) -168.615293.13584 -146.0216alpha) -79.496120.9176 -86.1904 Cu2S (sCuBr (s) -104.696.10648 -100.8344CuCl (s) -137.235286.1904 -119.8716CuCl2 (s) -205.8528108.07272 -161.9208CuCl2•2H2O (s) -821.3192167.36 -656.0512CuCN (s) 94.976889.99784 108.3656malachite) -1051.4392186.188 -893.7024 CuCO3•Cu(OH)2 (sCuF (s) -192.46464.852 -171.544CuF2 (s) -548.940868.6176 -499.1512CuFe2O4 (s) -965.20696141.0008 -858.80784CuFeO2 (s) -532.623288.7008 -479.9048CuI (s) -67.780896.6504 -69.4544CuN3 (s) 279.0728100.416 344.7616CuO (s) -157.318442.63496 -129.704CuS (s) -53.136866.5256 -53.5552CuSO4 (s) -771.36224108.784 -661.9088CuSO4•3H2O (s) -1684.31104221.3336 -1400.1756CuSO4•5H2O (s) -2279.6524300.4112 -1880.055296CuSO4•H2O (s) -1085.83168146.0216 -918.22064F (g) 78.99392158.6572861.9232-262.3368 F-1 (g) -255.6424145.47768F2 (g) 0202.7148 0alpha) 027.27968 0 Fe (s11.049944 Fe (l) 13.12939234.28788Fe(CN)6-3 (aq) 561.9112270.2864 729.2712Fe(CN)6-4 (aq) 455.637694.9768 694.92056Fe(CO)5 (l) -774.04338.0672 -705.4224Fe(CO)5 (g) -733.8736445.1776 -697.2636Fe(OH)+2 (aq) -290.788-142.256 -229.40872Fe+2 (aq) -89.1192-137.6536 -78.8684Fe+3 (aq) -48.5344-315.892 -4.6024Fe2(SO4)3 (s) -2581.528307.524 -2263.1256hematite) -824.24887.40376 -742.2416 Fe2O3 (sfayalite) -1479.8808145.1848 -1379.0464 Fe2SiO4 (salpha-cementite) 25.104104.6 20.0832 Fe3C (smagnetite) -1118.3832146.44 -1015.4568 Fe3O4 (sFe3Si (s) -93.7216103.7632 -94.5584Fe4N (s) -10.46156.0632 3.7656pyrrhotite) -736.384485.7624 -748.5176 Fe7S8 (sFeAl2O4 (s) -1966.48106.2736 -1849.328FeAsS (s) -41.84121.336 -50.208FeBr2 (s) -249.7848140.66608 -237.2328FeCl2 (s) -341.79096117.94696 -302.33584FeCl3 (s) -399.48832142.256 -334.05056siderite) -740.56892.8848 -666.7204 FeCO3 (sFeCr2O4 (s) -1444.7352146.0216 -1343.9008FeF2 (s) -702.91286.98536 -661.072FeF3 (s) -1041.81698.324 -970.688FeI2 (s) -104.6167.36 -112.968FeMoO4 (s) -1075.288129.2856 -974.872FeO (s) -271.9660.75168 -251.4584FeOH+1 (aq) -324.6784-29.288 -277.3992strengite) -1888.2392171.25112 -1657.7008 FePO4•2H2O (spyrrhotite) -99.997660.29144 -100.416 FeS (spyrite) -178.238452.9276 -166.9416 FeS2 (sFeSi (s) -73.638446.024 -73.6384beta-lebanite) -81.169655.6472 -78.2408 FeSi2 (sFeSO4 (s) -928.4296120.9176 -825.0848FeSO4•7H2O (s) -3014.572409.1952 -2510.27448FeWO4 (s) -1154.784131.796 -1054.368FNO3 (g) 10.46292.88 73.6384Fr (s) 094.14 0Fr (g) 72.8016181.92032 46.6516Fr2O (s) -338.904156.9 -299.156H+1 (aq) 00 0H2 (g) 0130.586824 0 H2AsO4-1 (aq) -909.55976117.152 -753.28736 H2CS3 (l) 25.104223.0072 27.8236 H2MoO4 (g) -851.0256355.64 -787.4288-228.588656 H2O (g) -241.818464188.715136-237.178408 H2O (l) -285.8299669.91464H2O2 (g) -136.10552232.88144 -105.47864 H2O2 (l) -187.77792109.6208 -120.41552 H2PO4-1 (aq) -1296.2868890.3744 -1130.39128 H2S (g) -20.16688205.76912 -33.0536 H2Se (g) 29.7064218.90688 15.8992 H2Se (g) 29.7064218.90688 15.8992 H2SiO3 (s) -1188.6744133.888 -1092.4424 H2SO4 (l) -813.9972156.9 -690.06712 H2SO4 (g) -740.568289.1144 -656.0512 H2VO4-1 (aq) -1174.0304121.336 -1020.896 H2WO4 (s) -1131.772146.44 -1004.16 H2WO4 (g) -905.4176351.456 -839.7288 H3BO3 (s) -1094.325288.82632 -969.0144 H3PO4 (l) -1254.3632150.624 -1111.6888 H3PO4 (s) -1266.9152110.54128 -1112.5256 H4SiO4 (s) -1481.136192.464 -1333.0224 HAsO4-2 (aq) -906.33808-1.6736 -714.71088 orthorhombic) -788.7676850.208 -721.74 HBO2 (smonoclinic) -794.2487237.656 -723.4136 HBO2 (s-53.51336 HBr (g) -36.44264198.61448-95.31152 HCl (g) -92.29904186.77376HClO (g) -92.048236.6052 -79.496 HCN (g) 135.1432201.6688 124.6832 HCN (l) 108.86768112.84248 124.93424 HCO3-1 (aq) -691.9917691.2112 -586.84784 HCrO4-1 (aq) -878.2216184.096 -764.8352 He (g) 0126.038816 0-273.2152 HF (g) -271.1232173.67784Hg (l) 076.02328 031.852792 Hg (g) 61.31652174.84936Hg(CH3)2 (l) 59.8312209.2 140.164 Hg(CH3)2 (g) 94.39104305.432 146.0216 Hg2(N3)2 (s) 594.128205.016 746.4256 Hg2Br2 (s) -206.8988218.73952 -181.075152 Hg2Cl2 (s) -265.22376192.464 -210.777368 Hg2CO3 (s) -553.5432179.912 -468.1896 Hg2F2 (s) -485.344158.992 -426.768 Hg2I2 (s) -121.336242.672 -111.00152 Hg2SO4 (s) -743.12024200.66464 -625.880376 HgBr2 (s) -170.7072170.33064 -153.1344HgCl (g) 84.0984259.78456 62.76 HgCl2 (s) -224.2624146.0216 -178.6568 HgF2 (s) -422.584116.3152 -372.376 HgH (g) 239.99424219.49264216.01992 HgI (g) 132.38176281.41584 88.44976 HgI2 (g) -17.1544336.01704 -59.8312 HgI2 (sred) -105.4368181.1672 -101.6712-58.425376 HgO (syellow) -90.4580871.128HgO (s red hexagonal) -89.537671.128 -58.24128 HgO (s red orthorhombic) -90.8346470.2912 -58.55508 HgS (sred) -58.157682.4248 -50.6264black) -53.555288.2824 -47.6976 HgS (sHgSe (g) 75.7304267.02288 31.38 HgSe (s) -46.02494.14 -38.0744 HgTe (s) -33.8904106.692 -28.0328 HI (g) 26.48472206.4804 1.71544 HN2O2-1 (aq) -39.3296142.256 76.1488 HN3 (g) 294.1352238.86456 328.0256 HNCO (g) -116.7336238.11144 -107.36144 HNCS (g) 127.612247.6928 112.968 cis) -76.5672249.32456 -41.84 HNO2 (gtrans) -78.6592249.1572 -43.932 HNO2 (gHNO3 (l) -173.2176155.60296 -79.9144 HNO3 (g) -135.05952266.26976 -74.76808 HOF (g) -98.324226.64728 -85.64648 HPO4-2 (aq) -1292.14472-33.472 -1089.26256 HReO4 (s) -762.3248158.1552 -664.8376 HS-1 (aq) -17.572862.76 12.04992 HSe-1 (aq) 15.899279.496 43.932 HSeO3-1 (aq) -514.54832135.1432 -411.53824 HSeO3-1 (aq) -514.54832135.1432 -411.53824 HSeO4-1 (aq) -581.576149.3688 -452.2904 HSeO4-1 (aq) -581.576149.3688 -452.2904 HSO3-1 (aq) -626.21928139.7456 -527.8116 HSO3F (g) -753.12297.064 -690.36 HVO4-2 (aq) -1158.96816.736 -974.87270.282832I (g) 106.83844180.681856-51.58872 I-1 (aq) -55.18696111.2944I2 (s) 0116.135288 0 I2 (g) 62.437832260.5795219.359368 IBr (g) 40.83584258.663248 3.72376 ICl (l) -23.89064135.1432 -13.598 ICl (g) 17.782247.44176 -5.4392-22.34256 ICl3 (s) -89.5376167.36-118.49088 IF (g) -95.64624236.06128-771.5296 IF5 (g) -840.1472334.72IF7 (g) -943.9104346.4352-818.3904149.7872 IO (g) 175.05856245.3916IO-1 (aq) -107.5288-5.4392 -38.4928 IO3-1 (aq) -221.3336118.4072 -128.0304 K (g) 89.119290.03968 60.668 K (l) 2.28446471.462720.263592 K (s) 064.68464 0 K2B4O7 (s) -3334.2296208.3632 -3136.7448 K2CO3 (s) -1150.1816155.51928 -1064.4096 K2O (s) -363.171294.14 -322.168 K2O2 (s) -495.804112.968 -429.6968 K2SiO3 (s) -1548.08146.14712 -1455.6136 K2SO4 (s) -1433.68944175.728 -1316.37008 K3AlCl6 (s) -2092376.56 -1938.4472 KAl(SO4)2 (s) -2465.38016204.5976 -2235.46936 KAl(SO4)2•12H2O (s) -6057.34416687.4312 -5137.1152 KAlCl4 (s) -1196.624196.648 -1096.208 KBF4 (s) -1886.984133.888 -1784.8944 KBH4 (s) -226.7728106.60832 -159.8288 KBO2 (s) -994.955279.99808 -978.6376-379.19592 KBr (s) -392.1663296.4412KBrO3 (s) -332.2096149.1596 -243.5088 KCl (s) -435.8891282.67584-408.31656-235.1408 KCl (g) -215.8944239.49216KClO3 (s) -391.204142.96728 -289.90936 KClO4 (s) -430.1152151.0424 -300.4112-102.04776 KCN (s) -113.47008127.77936-538.8992 KF (s) -568.605666.56744 KF•2H2O (s) -1158.968150.624 -1015.4568-34.05776 KH (s) -57.8228850.208KH2AsO4 (s) -1135.956155.14272 -991.608 KHF2 (s) -931.3584104.26528 -863.1592-322.29352 KI (s) -327.64904106.39912KIO3 (s) -508.356151.4608 -425.5128 KMnO4 (s) -813.3696171.71136 -713.7904 KNO3 (s) -492.70784132.92568 -393.12864 KO2 (s) -284.512122.5912 -240.58 KOH (s) -425.8475278.8684 -379.0704 Kr (g) 0163.975144 0128.0304 Li (g) 160.6656138.657760.933032 Li (l) 2.38069633.93224Li (s) 0160.6656 0 Li2B4O7 (s) -3363.936155.6448 -3171.472 Li2BeF4 (s) -2273.5856130.5408 -2171.496 Li2CO3 (s) -1216.0377690.1652 -1132.1904 Li2O (s) -598.730437.90704 -561.9112。
(化工热力学)第4章偏摩尔性质、逸度和活度

4.2.4 Gibbs-Duhem方程
n 1. Gibbs-Duhum Eq的一般形式 对溶液的热力学性质有下面两个表达形式:
nM mT , p, n1, n2 ,, nN
nM ni Mi
对这两个式子,分别求全微分:
30
dnM
nM
T
p,n
dT
nM
p
T
,ndpΒιβλιοθήκη M i dnidnM nidMi Midni
第4章 偏摩尔性质、逸度和活度
1
u 第3章学习了纯物质及均相定组成系统的热力学性质。
M f T , p
u 热力学更多的实际应用是涉及多组元混合物的均相 敞开系统。
u 由于混合物的组成常因为质量传递或化学反应而发 生变化,所以在用热力学来描述混合物时必须考虑 组成对其性质的影响。
M f T, p, xi
nM mT , p, n1, n2 ,...nN
dnM
nM
T
p,n
dT
nM
p
T
,n
dp
N i 1
nM
ni
T , p,nji
dni
定义:
Mi
nM ni
T , p,nji
Mi
18
注意:
1. 偏摩尔量的物理意义是:在T,p,及其他组元量nj 不变的情况下,向无限多的混合物中加入1mol组分i 所引起的混合物广度热力学性质的变化。其三要素 为:恒温恒压、广度性质、随组分i摩尔数的变化率。
dnG nV dp nS dT idni
10
注意:以上关系式的使用情况
n 1 适用于敞开体系,封闭体系;
n 2 当dni=0时,简化成适用于定组成、定质量 体系;
制冷剂的热力学性质表

-10 0.2191 0.7001 0.0766 190.82 347.14 156.32 0.9660 1.5600
-5
0.2610 0.7078 0.0650 195.39 349.43 153.93 0.9831 1.5571
(一) R12 制冷剂饱和状态热力性质表 2
温度 绝 对 压 比容
焓
-35 0.0807 0.6656 0.1954 168.37 335.85 167.48 0.8768 1.5800
-30 0.1004 0.6720 0.1594 172.81 338.15 165.34 0.8952 1.5751
-29.792 0.10044 0.6723 0.1582 172.99 338.24 165.25 0.8959 1.5760
(三) R134a 制冷剂饱和状态热力性质表 2
温度 绝 对 压 比容
焓tBiblioteka 力P液体 v/ 蒸气 v// 液体 h/
(℃) (MPa) (dm3/kg) (m3/kg) (kJ/kg)
熵
汽化热 r
蒸气// (kJ/kg) 液体 S/ 蒸气 S//
(kJ/kg)
(kJ/kg·K) (kJ/kg·K)
10
10 0.6809 0.8021 0.0346 211.76 408.17 196.41 1.0419 1.7352
20 0.9101 0.8265 0.0259 223.86 411.18 187.32 1.0833 1.7222
30 1.1912 0.8541 0.0197 236.38 413.74 177.36 1.1243 1.7092
-30 0.1639 0.7262 0.1352 166.25 392.63 226.38 0.8702 1.8014
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式中 a 、 b 的意义与 e 的表达式中相同, t 和 T 分别是 摄氏和 K 氏温标下的气温。
5.饱和差 e
d
空气的饱和水汽压与实际水汽压之差。
ed es e
这个参量用得较少。
hPa
(4.1.3)
6.绝对湿度 a 单位容积里水汽的含量,也称水汽密度 v
v
e e 217 克 / 米3 RT T v
Mv
622
e 克 / 千克 Pe
(4.1.9)
M v , M d 分别为湿空气中的水汽和干空气的质量
v , d 分别为水汽和干空气的的密度 P 为气压, e 为水汽压,均以 hPa 为单位。
10.相对湿度 RH 实际水汽压与同温下饱和水汽压之比。
RH
e es
100%
(4.1.11)
ed es e
二、已知 t , RH , P ,求其他各种相应的湿度参理 (1) T 273.16 t
(2)求饱和水汽压 es ,单位 hPa
a T 273.16 es 6.1078e x p Tb
(3)求水汽压 e ,单位 hPa
e
RH es 100
该参量是一个重要的湿度参量,在诊断分析中经常 要用到,有时也要用它来计算其他的温湿参量。 如果 q 以克/千克为单位,则(4.1.6)式写成
q
622e p 0.378e
(4.1.7)
式中 p , e 仍以 hPa 为单位。
8.饱和比湿 qs 饱和湿空气中含有的水汽与湿空气质量之比。
qs 0.622es 克 / 克 p 0.378es
622es 克 / 千克 p 0.378es
式中 P 为气压,es 为饱和水汽压,可由(4.1.2)式求得, 单位均用 hPa 。
这是一个温度的函数,与大气的实际湿度无关,一般不 单独用在诊断分析中,但有时要用它来计算别的参量。
9.混合比W 湿空气中的水汽质量与其中干空气质量之比。
W
v e / RvT Rd e M d d Pd / R dT Rv P e e 0.622 克/克 Pe
常用的参量有:
露点 T , 温度露点差 T Td ,
d
水气压 e , 绝对湿度 a (也称为水汽密度 v ), 比湿 q , 混合比 W , 相对温度 RH 饱和差 d 等等
1.露点(或称露点温度) Td
空气在定压冷却过程中,发生凝结现象时的温度。 这在日常工作中最容易从地面天气报告、气压表、高空 压温湿记录月报表等资料来源中获得的温度特征参量。
q
622e p 0.378e
求饱和比湿 qs ,单位克/千克
qs
622es p 0.378es
(7)求绝对湿度 a ,单位克/米 3
a 217e T
(8)求混合比W ,单位克/千克
W
622e pe
(9)求相对湿度 RH ,单位%
RH 100e es
(10)求饱和差 ed ,单位 hPa
(3)求水汽压 e ,单位 hPa 。 a Td 273.16
e 6.1078e x p Td b
(4)求饱和水汽压 es ,单位 hPa 。
a T 273.16 es 6.1078e x p Tb
(5)求比湿 q ,单位克/千克
可以用它来比较不同气压情况下空气质块的热力 差异,来分析大气的稳定度状况;
在使用位温分析天气问题时,一定要注意天气过程 是否满足绝热条件或者近于满足绝热条件,因此在伴有 降水或天气过程中有明显的非绝热增温的情况下,最好 考虑位温的变化或者改用其他更具保守性的温湿参数。
4 热力学参量的计算
4.1 湿度参量的计算
பைடு நூலகம்
王咏青 南京信息工程大学
天气学诊断中一个重要内容是借助温、湿特征参量的分 析,来揭露某些天气事实,或说明某些想陈述清楚的问 题。
这些特征参量有些是能从气象记录中直接取得的, 如在地面天气观测报告中,能得到温度T 和露点 T ;
d
在探空报告电码中,能得到温度T 和温度露点差T T 。 后者通过简单换算,也可以变成温度和露点两项。
d
迭代法计算露点温度
原理 1、饱和水汽压的计算可由下列经验公式给 出:
es 6.1078exp a(T 273.16) /(T b)
当Td >273.16 时,即水面有a=17.26;b=35.86 当Td <=273.16时,即冰面有a=21.87;b=7.66
t 15 C
e 6.1078exp Td b atd 6.1078exp 273.16 td b
hPa (4.1.1)
上式中: td 为摄氏温标下的露点温度,单位℃。
Td 为
K 氏温标下的露点温度,单位 K
a 、 b 为常数,且:
在水面上, a 17.2693882; b 35.86 在冰面上, a 2 1 .8 7 4 5 5 8 4; b 7 .6 6
4.饱和水汽压 饱和湿空气中水汽压的分压强。所谓饱 和湿空气就是指露点、气温相等的空气,于 是
a T 273.16 e 6.1078e x p Tb at 6.1078 e x p273.16 t b
hPa
(4.1.2)
式中,e 是实际水汽压,es 是同温下的饱和水汽压。
RH
也可取以下近似表达式:
q qs 100%
RH
W Ws
100%
(4.1.12)
§ 4.2 湿度参数的计算步骤
一、已知 t, td , p ,求其他各种相应的湿度参量
(1) T 273.16 t (2) Td 273.16 td 或 Td 273.16 td t td
一般情况下, q 4 10
克/克,所以 C p 的值总在 0.288 和 0.285 之间变化,变化范围很小,日常计算中选取
R Cp 0.286 较为适合,因此
2
R
P0 T P
0.286
(4.3.2)
上式是常用的位温计算公式。
位温是一个重要的温度参量,在干绝热过程中位温 是守恒的。
计算框图:
开始 读入 Rh, T, P,
es=6.1078exp(a(T-273.16)/(T-b))
e=es×Rh/100
否
e<es
是
Td=T
输出 Td
结束
Td=T-0.05 es=6.1078exp(a(T-273.16)/(T-b))
§4.3 温度参量的计算
单纯的温度特征参量比较少,除了平常所说的气温 T 之 外,只有位温 。
R 是气体常数,且有关系式
R Rd 1 0.61q
式中 Rd 是干空气气体常数, R 287 焦耳/度· 千 克
q 是湿空气比湿。
C p 是定压比热,C p C pd 1 0.85q ,对于干空气来说,
C pd 1004 焦耳/度· 千克
R Cp
Rd 1 0.61q R 1 0.24q d C pd C pd 1 0.85q
位温 是气块从它原有的温度和压强经绝热膨胀或 压缩到标准气压时所具有的温度,标准气压常取 1000 hPa 。
位温的表达式为:
P T 0 P
R/Cp
(4.3.1)
其中:T 是空气的绝对温度,单位 K
P0 是标准气压,常取 1000 hPa
p 是气块原有压强,单位为 hPa
d
td t t td
(4.1)
在天气学研究中仅仅有温度T 和露点T 两个温湿参量 还不够,有时还需要其他形式的温湿特征参量如比湿
d
q 、位温 、相当位温e 等等。
计算温湿特征参量是今后从事天气学研究工作必须具 备的基本功。
§4.1 湿度参量的计算
气象学中根据研究对象的差异对湿度采用了许多不 同的表示方式。
o
水面 冰面
t 40 C
o
相对湿度 RH (单位:%)
RH e / es *100
已知温度、相对湿度、气压求露点
1、在未饱和的湿空气中,露点温度总低于气 温,故可先假设温度T为露点温度的初值 Td0,用Td0计算es的初值,用相对湿度的公式 计算e; 2、如果 e es ,则说明露点温度的初值偏 高于实际值,可从初值上减去0.05,并作为 新的初值 3、重复1、2、,直到e第一次大于es为止,此时 的T即为露点温度。
0.217
e 千克 / 米3 T
(4.1.4)
推导见《大气物理 式中: e 是水汽压,以 hPa 为单位;学》,北京大学出版 社,2003,P22
绝对湿度也可以用下式计算:
a 0.734e 克 / 米3 1 0.00366t
(4.1.5)
式中: e 是水汽压,以 hPa 为单位
t 是摄氏温标下的温度,℃为单位。
(9)求露点 Td
原则上讲,可以通过 e 的表达式:
a Td 273.16 e 6.1078e x p Td b
反求出露点 Td ,但这样做计算太复杂,实际工作中很少 采用。
下面介绍一种简单的迭代法求 Td ,可在计算机上很快地 实现。
三、已知相对湿度 RH ,用迭代法求取露点T
这个参量用得较少。
7.比湿 q 湿空气中含有水汽质量与湿空气质量之比。
q
M v v 0.622e 克/克 M p 0.378e
(4.1.6)