Name: temperature effects on gibbs free energy
Uploaded: 2023-04-30T18:28:32.000Z
Duration: 2 min 23 s
Channel: JoVE

K12 Standards

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High School

Chemistry

Matter And Its Interactions

HS-PS1-6

gibbs-free-energy-and-thermodynamic-favorability

Gibbs Free Energy and Thermodynamic Favorability

吉布斯自由能的变化，即ΔG，是指在储存能量的化学键形成或断裂时分别吸收或释放的能量。
Δ 的符号 G 取决于焓、熵和温度的符号及其相对数值。
如果 ΔH 为负值且 ΔS 为正值，则在所有温度下 ΔG 均为负值。因此，系统熵增加的放热反应总是自发进行的。
如果焓变 ΔH 和熵变 ΔS 均为负值，则吉布斯自由能变 ΔG 取决于温度。只有在低温下，焓变和熵变均为负的反应才能自发进行。
Delta G 也依赖于温度，如果两个 delta H 和 delta S 焓变和熵变均为正值的反应仅在较高温度下自发进行。
当 ΔH 为正值且 ΔS 为负值时，ΔG 恒为正值，反应在所有温度下均为非自发反应。
对于任何反应混合物组成，该反应的吉布斯自由能变化 ΔG 等于标准自由能与 RT 乘以反应商的自然对数之和。
当反应物和产物处于平衡状态时，自由能变化为零，反应商等于平衡常数。因此，标准自由能变化等于负的 RT ln(K)。
如果 ΔG° 小于零，则 ln(K) 为正值，意味着 K 大于 1。在此情况下，平衡时有利于产物的生成。平衡常数越大，吉布斯自由能的降低幅度就越大。
具有负ΔG值的反应会向环境释放自由能，称为“放能反应”。
相反，如果 ΔG° 大于零，则 ln(K) 为负值，意味着 K 小于 1，反应的逆向进行占优势。
具有正ΔG的反应会从环境中吸收自由能，这类反应称为“吸能反应”。

吉布斯自由能和热力学有利性

过程的自发性取决于系统的温度。 例如，相变将自发地沿一个方向或另一个方向进行，具体取决于所讨论物质的温度。 同样，一些化学反应也可以表现出与温度相关的自发性。 为了说明这个概念，考虑自由能变化与过程的焓和熵变化相关的方程:


 <img alt="Eq1" src="/files/ftp_upload/11694/11694%20PT%20eq%201.svg" style="text-align: center; height: 15px;">


 过程的自发性（反映在其自由能变化的算术符号中）由焓和熵变化的符号以及在某些情况下的绝对温度决定。 由于 T 是绝对（开尔文）温度，因此它只能为正值。 因此，关于焓变和熵变的迹象，存在四种可能性:


 <ol>
 <li>ΔH 和 ΔS 均为正值。 该条件描述了涉及系统熵增加的吸热过程。 在这种情况下，如果 TΔS 项的大小大于 ΔH，则 ΔG 将为负。 如果 TΔS项小于 ΔH，则自由能变化将为正。 这种过程在高温下是自发的，在低温下是非自发的。</li>
 <li>ΔH 和 ΔS 均为负值。 该条件描述了涉及系统熵减少的放热过程。 在这种情况下，如果 TΔS 项的大小小于 ΔH，则 ΔG 将为负。 如果 TΔS 项的大小大于 ΔH，则自由能变化将为正。 这种过程在低温下是自发的，在高温下是非自发的。</li>
 <li>ΔH 为正，ΔS 为负。 该条件描述了涉及系统熵减少的吸热过程。 在这种情况下，无论温度如何，ΔG 都将为正。 这样的过程在所有温度下都是非自发的。</li>
 <li>ΔH 为负，ΔS 为正。 该条件描述了涉及系统熵增加的放热过程。 在这种情况下，无论温度如何，ΔG 都将为负。 这样的过程在所有温度下都是自发的。</li>
 </ol>


 过程的自由能变化可以被视为其驱动力的度量。 ΔG的负值表示正向过程的驱动力，而正值表示反向过程的驱动力。 当ΔGrxn为零时，正向和反向驱动力相等，并且该过程以相同的速率在两个方向上发生（系统处于平衡状态）。



 回想一下，Q是系统质量作用表达式的数值，它的值可用于确定反应进行以达到平衡的方向。 当 Q小于平衡常数 K 时，反应将以正向进行，直至达到平衡且 Q=K。相反，如果 Q&gt; &gt;K，则反应将以相反方向进行，直至达到平衡。



 在非标准条件（压力不是 100 kPa;浓度不是 1 M）下，反应物和产物发生的过程的自由能变化与根据以下方程的标准自由能变化相关:


 <img alt="Eq2" src="/files/ftp_upload/11694/11694%20PT%20eq%202.svg" style="text-align: center; height: 18px;">


 R 是气体常数 (8.314 J/K mol)，T 是开尔文温度或绝对温度，Q是反应商。 对于处于平衡状态的系统，Q=K 且 ΔG = 0，前面的方程可以写为


 <img alt="Eq3" src="/files/ftp_upload/11694/11694%20PT%20eq%203.svg" style="text-align: center; height: 18px;">


 <img alt="Eq4" src="/files/ftp_upload/11694/11694%20PT%20eq%204.svg" style="text-align: center; height: 18px;">


 这种形式的方程提供了这两个基本热力学性质之间的有用联系，并且可用于从标准自由能变化导出平衡常数，反之亦然。 标准自由能变化与平衡常数之间的关系总结如下。


 如果 K &gt; 1，则 ΔG° &lt; 0，并且反应混合物中的产物更加丰富。


 如果 K &lt; 1，则 ΔG° &gt; 0，并且反应混合物中的反应物更加丰富。


 如果 K = 1，则 ΔG° = 0，并且反应混合物中的反应物和产物相对丰富。


 本文改编自 <a href="https://openstax.org/books/chemistry-2e/pages/16-4-free-energy">Openstax, Chemistry 2e, Section 16.4: Free Energy.
</a>

过程的自发性取决于系统的温度。例如，相变在某一方向上会自发进行……

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Organic Chemistry

有机化学

Unit 1

第一单元

Thermodynamics and Chemical Kinetics

热力学与化学动力学

KEY TERMS AND CONCEPTS

关键术语与概念

temperature effects on gibbs free energy

Temperature changes can decide whether a process is spontaneous. This idea applies to phase changes and to some chemical reactions. The key link is Gibbs free energy, which connects free energy change with enthalpy and entropy.

The sign of the Gibbs free energy change, or ΔG, depends on the signs of enthalpy change (ΔH) and entropy change (ΔS), and sometimes on the absolute temperature. Because temperature is measured in kelvin, it is always a positive value. That means there are four main sign combinations to consider.

If both ΔH and ΔS are positive, the process is endothermic and the system gains entropy. In this case, ΔG is negative only when the TΔS term is larger than ΔH. So the process is spontaneous at high temperatures and nonspontaneous at low temperatures. If both ΔH and ΔS are negative, the process is exothermic and the system loses entropy. Then ΔG is negative when the TΔS term is smaller than ΔH, which makes the process spontaneous at low temperatures and nonspontaneous at high temperatures.

If ΔH is positive and ΔS is negative, the process is endothermic and the system becomes less disordered. In that case, ΔG stays positive at any temperature, so the process is nonspontaneous at all temperatures. If ΔH is negative and ΔS is positive, the process is exothermic and the system becomes more disordered. Then ΔG stays negative at any temperature, so the process is spontaneous at all temperatures.

Gibbs free energy also shows the driving force of a process. A negative ΔG means the forward direction is favored. A positive ΔG means the reverse direction is favored. When ΔGrxn is zero, the forward and reverse driving forces are equal, and the system is at equilibrium.

The reaction quotient, Q, helps predict which way a reaction will shift to reach equilibrium. When Q is less than the equilibrium constant, K, the reaction moves forward until Q = K. When Q is greater than K, the process moves in reverse until equilibrium is reached. Under nonstandard conditions, the free energy change is related to the standard free energy change by ΔG = ΔG° + RT ln Q, where R is the gas constant and T is the kelvin temperature.

At equilibrium, Q equals K and ΔG is zero, so the equation can be written as a link between ΔG° and K. This relationship lets chemists find equilibrium constants from standard free energy changes, or the reverse. If K is greater than 1, ΔG° is negative and products are more abundant. If K is less than 1, ΔG° is positive and reactants are more abundant. If K equals 1, ΔG° is zero and reactants and products are present in similar amounts.

Temperature Effects on Gibbs Free Energy

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Temperature changes can decide whether a process is spontaneous. This idea applies to phase changes and to some chemical reactions. The key link is Gibbs free energy, which connects free energy change with enthalpy and entropy. The sign of the Gibbs free energy change, or ΔG, depends on the signs of enthalpy change (ΔH) and entropy change (ΔS), and sometimes on the absolute temperature. Because temperature is measured in kelvin, it is always a positive value. That means there are four main...

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Temperature Effects on Gibbs Free Energy

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