什么是焓?定义、方程式、单位、例子
热力学是研究功、热、温度和能量之间关系的科学分支。每天我们都会遇到包括辐射和吸收热量的事件,例如“冰融化时”。焓是一个状态函数,所以要研究焓是什么,我们需要了解什么是状态函数。
什么是状态函数?
基本上,可以通过加热或冷却来改变物质的温度。所以,在状态函数中,重要的是只改变温度,不考虑方式或路径。因此可以说State函数只依赖于当前状态/初始状态和最终状态。
状态函数的一些示例是温度、压力、内能、焓等。
内能 (U)
每种物质都包含一定数量的能量存储在其中,这种能量只不过是物质(系统)的内部能量,用U表示。物质内部的能量是所有动能和势能以及存在于物质粒子中的所有其他能量的总和。
因此,内能的变化可以表示为:
ΔU = Q + W
在哪里:
- Q是物质与周围环境之间的热传递,
- W是完成的工作。
这也被称为热力学第一定律。
等压过程
在热力学中,当系统的压力在整个过程中保持恒定时,称为等压过程。于是,热力学第一定律变为
ΔU = Q p – P ex × ΔV
要么
Q p = ΔU + P ex × ΔV
在哪里:
- Q p是在等压过程中所做的功,并且
- P ex外部压力。
焓 (H)
Enthalpy is simply defined as the sum of internal energy and the energy that is resulted due to its pressure and volume.
因此,焓可以表示为:
H = U + PV
在哪里:
- U是内能,
- P是压力和
- V是体积。
这里,U、P 和 V 是状态函数,因此 H 也是状态函数。由于焓是一个状态函数,焓的变化(ΔH)将取决于系统的初始状态和最终状态
ΔH = H 2 – H 1
这里,H 1是系统在初始状态的焓,H 2是系统在最终状态的焓。所以如果我们用类似的形式写出焓的公式(H = U + PV)
H 1 = U 1 + P 1 V 1和 H 2 = U 2 + P 2 V 2
所以如果我们把上面的方程放在我们得到的 ΔH 中,
ΔH = (U 2 + P 2 V 2 ) – (U 1 + P 1 V 1 )
ΔH = U 2 + P 2 V 2 – U 1 -P 1 V 1
ΔH = (U 2 – U 1 ) + (P 2 V 2 -P 1 V 1 )
ΔH = ΔU + Δ(PV)
在哪里:
- ΔU 是内能的变化,
- Δ(PV)是压力和体积的变化。
现在,在恒定压力下 P1 = P2 = P
ΔH = ΔU + PΔV
考虑该等压过程的内外压力相同(即 P ex = P),则等压过程的公式将变为,
Q p = ΔU +PΔV
因此,从上述两个等式,我们得到,
ΔH = Q p
因此,从这个导出的公式中,我们了解到系统焓的增加等于它在恒定压力下吸收的热量。
化学反应的ΔH和ΔU之间的关系
在恒定压力下,ΔH 和 ΔU 由等式 ΔH = ΔU + PΔV 相关。对于固体和液体之间的反应,ΔV 非常小,因为随着压力的变化,固体或液体不会受到显着影响。因此,对于这些反应,从方程中删除 PΔV 并写出 ΔH = ΔU
但是,对于容易受压力变化影响的涉及气体的反应,应严格考虑ΔV。
ΔH = ΔU + PΔV
ΔH = ΔU + P(V 2 – V 1 )
ΔH = ΔU + PV2 – PV1
在哪里:
- V 1是初始状态(气体反应物的体积)和
- V 2是最终状态(气体产品的体积)。
这里我们认为反应物和产物是理想的,所以我们可以使用理想气体方程(PV = nRT)。
假设有 n 1摩尔的气态反应物产生 n 2摩尔的气态产物。那么方程变为
PV 1 = n 1 RT 和 PV 2 = n 2 RT
因此,方程变为
ΔH = ΔU + n 2 RT – n 1 RT
ΔH = ΔU + RT (n 2 – n 1 )
ΔH = ΔU + RT Δn
Requirements for ΔH to be equal to ΔU
- When the reaction is conducted inside a closed container which prevents the alter of the volume of the system (ΔV = 0). Then change in enthalpy will change as ΔH = ΔU.
- When there is only solids or liquids involved in the reactions then we can neglect ΔV as the change in them due to the pressure is significant. So, ΔH = ΔU.
There reaction in which the moles of gaseous products and reactants are same (i.e. n2 = n1). So, ΔH =ΔU
在化学反应中所做的工作
在恒定压力和温度下所做的功由下式给出
W = – P ex × ΔV
假设 P ex = P,则方程变为
W = -P( V 2 – V 1 )
W = PV 1 – PV 2
使用理想气体方程,
W = n 1 RT – n 2 RT
W = -RT (n 2 – n 1 )
W= – RT Δn
示例问题
问题 1:对于反应,系统吸收 10 kJ 的热量并对周围环境做 3 kJ 的功。系统的内能和焓有什么变化?
解决方案:
According to the First law of thermodynamics,
ΔU = Q + W
Q = +10 kJ and W = -3 kJ
(W = -3 kJ because the work is done on the surrounding by the system so the system has lose that energy)
ΔU = 10 kJ – 3 kJ
∴ ΔU = +7 kJ
and, Qp = ΔH
∴ Qp = +10kJ
Thus, the Internal energy increases by 7 kJ and Enthalpy by 10 kJ.
问题 2:对于一个反应,系统释放 5 kJ 的热量,系统做了 10 kJ 的功。系统的内能和焓有什么变化?
解决方案:
According to first law of thermodynamics,
ΔU = Q + W
Q = -5 kJ, W = +10 kJ
ΔU = -5 kJ +10 kJ = +5 kJ
and Qp = ΔH
∴Qp = -5 kJ
Thus, the Internal energy increases by 5 kJ and Enthalpy decreases by -5 kJ.
问题 3:理想气体在 3.036 x 10 5 Nm -2的恒定外部压力下从 5 dm 3的体积膨胀到 15 dm 3 。如果 ΔU 为 400 J,则求 ΔH。
解决方案:
ΔH = ΔU + PΔV
ΔH = ΔU + P(V2 – V1)
Assume that Pex = P, P =3.036 *105 N m-1
ΔU = 400 J
V1 = 5 dm3 = 5 × 10-3 m3
V2 = 10 dm3 = 15 × 10-3 m3
Substituting the values in the equation
ΔH = 400 J + 3.036 × 105 Nm-2 * (10 × 10-3 m3 – 5 × 10-3 m3)
ΔH = 400 J + 3.036 ×105 Nm-2 * (15 – 5) × 10-3 m3
ΔH = 400 J + 3.036 × 103 J
ΔH = 3436 J.
问题 4:计算在 420 K 恒压下使用 2 摩尔 HCl 时,下列反应所做的功。
4HCl (g) + O 2 (g) → 2Cl 2 (g) + 2H 2 O (g)
状态,无论所做的工作,是由系统还是在系统上。
解决方案 :
According to the Formula to calculate the work done in chemical reactions,.
W = – Δn RT
W = – RT ( n2 – n1 )
2 moles of HCl react with 0.5 mole of O2 to give 1 mole of Cl2 and 1 mole of H2O
Hence, n1 = 2.5,
n2 = 2,
R = 8.314 JK-1 mol-1
T = 420 K
Substituting the values in the equation,
W = – 8.314 J K-1 mol-1 × 420 K × (2 – 2.5) mol
W = -8.314 × 420 × (-0.5) J
W = 1745.94 J
概念问题
问题1:用例子解释状态函数。
回答:
Any property of a system whose value depends on the current state of the system and is independent of the path followed to reach that state is called the state function.
Example, Temperature.
问题2:简要解释内能。
回答:
Every substance is associated with a definite amount of energy. This energy is stored in a substance (System) is called its internal energy and is denoted by U. The internal energy is the sum of kinetic energies of all the molecules, ions and atoms of the system, the potential energies associated with the forces between the particles, the kinetic and potential energies of nuclei and electrons in the particles and the energy associated with existence of mass of the system.
问题3:如何计算焓的变化?
回答:
The change in enthalpy ( ΔH) can be obtained by
ΔH = ΔU + RT Δn
问题 4:什么是等压过程并给出任意 2 个例子。
回答:
Most chemical reactions are run in open containers under under constant pressure. In such reactions the volume of the system is allowed to change, such kind of processes are called as Isobaric processes.
Examples :
- Boiling of water and its conversion into steam,
- Freezing of water into ice.
问题 5:解释热力学第一定律并给出其数学方程。
回答:
First law of thermodynamics is simply the law of conversation of energy. According to this law the total energy of a system and its surroundings remain constant when the system changes from initial state to final state. The law is stated in different ways but the meaning is the same that the energy is conserved in all the changes.
Mathematical expression for the First Law of Thermodynamics,
ΔU = Q + W