Diverse novel species containing peroxo bonds are prepared using different methods.

Compound $\bf A$ can be prepared by bubbling $\rm CO_2$ into a concentrated aqueous hydrogen peroxide solution containing $\rm KOH$, crystallizing, while controlling the temperature at $-5\degree\rm C$ to $-20\degree\rm C$.

Compound $\bf B$ can be prepared by adding potassium bicarbonate to saturation in a $30\%$ aqueous hydrogen peroxide solution, then adding a certain amount of ethanol, and cooling to crystallize, while controlling the temperature at $-10\degree\rm C$ to $-15\degree\rm C$.

Crystal structure determination and thermal analysis indicate that:
In the crystal of $\bf A$, there is only one type of anion;

In the crystal of $\bf B$, there is only one type of cation, one type of anion, and one type of neutral molecule.

$\bf A$ loses $30.3\%$ of its weight when heated above $160\degree \rm C$ (Reaction 1);

$\bf B$ loses $53.9\%$ of its weight when heated above $200\degree\rm C$ (Reaction 2).

The following statements are made:
1. The anion structure of $\bf A$ contains a mirror plane.

2. The ratio of the number of cations, anions, and neutral molecules in the composition of $\bf B$ is $1:1:1$.

3. The solid products of the thermogravimetric analysis of $\bf A,B$ are consistent.

4. The coefficient of $\rm H_2O$ in the equation of Reaction 2 (with coprime integer coefficients) is 3. (If there is no $\rm H_2O$ in the reaction equation, this statement is considered correct)

5. Arranging $\bf A \rm,K_2O_2,O_2F_2$ according to the length of the peroxo bond, the order is $\rm K_2O_2>O_2F_2>\bf A$.

What is the sum of the serial numbers of the correct statements?
利用不同的方法制得多种多样的含过氧键的新物种。
控制温度在 $-5
\degree\rm C$ 到 $-20\degree\rm C$，在含 $\rm KOH$ 的浓过氧化氢水溶液中通入 $\rm CO_2$，析晶，可制得化合物$\bf A$。  

控制温度在 $-10\degree\rm C$ 到 $-15\degree\rm C$，在 $30\%$ 的过氧化氢水溶液中加入碳酸氢钾至饱和，再加入一定量的乙醇，冷却析晶，可制得化合物$\bf B$。

晶体结构测定和热分析表明：  
$\bf A$的晶体中，阴离子仅有 1 种；

$\bf B$的晶体中仅有 1 种阳离子、1 种阴离子和 1 种中性分子。
  
$\bf A$加热至 $160\degree \rm C$ 以上失重 $30.3\%$（反应 1）；
  
$\bf B$加热至 $200\degree\rm C$ 以上失重 $53.9\%$（反应 2）。

有如下说法：  
1.$\bf A$的阴离子结构中存在镜面。

2.$\bf B$的组成中阳离子、阴离子、中性分子数目之比为 $1:1:1$。

3.$\bf A,B$热重分析的固体产物一致。

4.反应 2 的方程式（系数为互质整数）中 $\rm H_2O$的系数为3。（若反应方程式中没有 $\rm H_2O$，该说法视为正确）

5.将 $\bf A \rm,K_2O_2,O_2F_2$ 按照过氧键长度排序，顺序为 $\rm K_2O_2>O_2F_2>\bf A$。

正确说法的序号和为多少？
2
3
5
6
8
9
11
12
14
All of the above options are incorrect.
2
3
5
6
8
9
11
12
14
以上选项均不对
First consider the final product of thermogravimetric analysis. $\rm KHCO_3$ decomposes at $120\degree \rm C$, so the final solid product of thermogravimetric analysis is $\rm K_2CO_3$. The solid products of thermogravimetric analysis of $\bf A, B$ are consistent, so statement 3 is correct.

<Checkpoint>[The final solid products of thermogravimetric analysis of $\bf A, B$ are both $\rm K_2CO_3$](1)</Checkpoint>

Assume $\bf A$ has 2 potassium atoms, then its molecular weight is $138.31\div(1-0.303)=198.44$. Combining the preparation conditions of strong alkalinity, we know that $\bf A$ is $\rm K_2C_2O_6$.

<Checkpoint>[$\bf A$ is $\rm K_2C_2O_6$](1)</Checkpoint>

Its anion structure is two $\rm [CO_3^-]$ groups connected by a peroxo bond, similar to the structure of $\rm H_2O_2$, with a two-fold rotation axis, but no mirror plane or center of symmetry, so statement 1 is incorrect.

<Checkpoint>[The anion structure of $\bf A$ does not have a mirror plane](1)</Checkpoint>

Similarly, assume $\bf B$ has 2 potassium atoms, then its molecular weight is $138.31\div(1-0.539)=300.02$. Its cation is $\rm 2K^+$, and according to the preparation process, it is inferred that the anion is $\rm 2HOOCO_2^-$, and the remaining molecular weight of about $68$ is $\rm 2H_2O_2$, which is consistent with the description of the question, so $\bf B$ is $\rm KHCO_4\cdot H_2O_2$. Other compositions cannot satisfy the thermogravimetric data. The ratio of the number of cations, anions, and neutral molecules in the composition of $\bf B$ is $1:1:1$, so statement 2 is correct.

<Checkpoint>[$\bf B$ is $\rm KHCO_4\cdot H_2O_2$](2)</Checkpoint>

Reaction 2 is the decomposition of $\rm KHCO_4\cdot H_2O_2$, that is $\rm 2[KHCO_4\cdot H_2O_2]\rightarrow K_2CO_3+CO_2+3H_2O+2O_2$. The coefficient of $\rm H_2O$ is 3, so statement 4 is correct.

<Checkpoint>[$\rm 2[KHCO_4\cdot H_2O_2]\rightarrow K_2CO_3+CO_2+3H_2O+2O_2$](2)</Checkpoint>

The negative charges on the two oxygen atoms in $\rm O_2^{2-}$ have repulsive force, so the peroxo bond is the longest; in $\rm O_2F_2$, the lone pair electrons of oxygen are hyperconjugated with the antibonding orbital of the other oxygen-fluorine bond, which enhances the bond order of the peroxo bond, so the peroxo bond is the shortest; the hyperconjugation effect brought by the $\rm CO_2^-$ group in $\bf A$ is not as good as $\rm O_2F_2$. Therefore, the order of the peroxo bond length is $\rm K_2O_2>\bf A>\rm O_2F_2$, so statement 5 is incorrect.

<Checkpoint>[In $\rm O_2F_2$, the lone pair electrons of oxygen are hyperconjugated with the antibonding orbital of the other oxygen-fluorine bond, enhancing the bond order of the peroxo bond](1)</Checkpoint>

<Checkpoint>[Peroxo bond length order $\rm K_2O_2>\bf A>\rm O_2F_2$](1)</Checkpoint>

The correct statements are 2, 3, and 4, so the answer is option F.
先考虑热重分析最终产物，$\rm KHCO_3$ 在 $120\degree \rm C$分解，故热重分析的最终固体产物均为 $\rm K_2CO_3$，$\bf A,B$热重分析的固体产物一致，说法3正确。

<Checkpoint>[$\bf A,B$热重分析的最终固体产物均为 $\rm K_2CO_3$](1)</Checkpoint>

设$\bf A$有2个钾，则其分子量为$138.31\div(1-0.303)=198.44$，结合强碱性的制备条件，可知$\bf A$为 $\rm K_2C_2O_6$。

<Checkpoint>[$\bf A$为 $\rm K_2C_2O_6$](1)</Checkpoint>

其阴离子结构为两个 $\rm [CO_3^-]$ 基团通过过氧键相连，类似 $\rm H_2O_2$ 的结构，有二次旋转轴，没有镜面和对称中心，说法1错误。

<Checkpoint>[$\bf A$的阴离子结构不存在镜面](1)</Checkpoint>

同理设$\bf B$有2个钾，则其分子量为$138.31\div(1-0.539)=300.02$，其阳离子为 $\rm 2K^+$，根据制备过程推断阴离子为$\rm 2HOOCO_2^-$，剩余约$68$的分子量，为$\rm 2H_2O_2$，符合题目描述，故$\bf B$为 $\rm KHCO_4\cdot H_2O_2$。其他组成不能满足热重数据。$\bf B$的组成中阳离子、阴离子、中性分子数目之比为 $1:1:1$，说法2正确。

<Checkpoint>[$\bf B$为 $\rm KHCO_4\cdot H_2O_2$](2)</Checkpoint>

反应2是 $\rm KHCO_4\cdot H_2O_2$ 的分解，即 $\rm 2[KHCO_4\cdot H_2O_2]\rightarrow K_2CO_3+CO_2+3H_2O+2O_2$，$\rm H_2O$ 的系数为3，说法4正确。

<Checkpoint>[$\rm 2[KHCO_4\cdot H_2O_2]\rightarrow K_2CO_3+CO_2+3H_2O+2O_2$](2)</Checkpoint>

$\rm O_2^{2-}$ 中两个氧原子上的负电荷之间具有排斥力，因此过氧键最长；$\rm O_2F_2$  中氧的孤对电子与另一氧氟键的反键轨道超共轭，增强过氧键键级，因此过氧键键最短；$\bf A$中 $\rm CO_2^-$ 基团带来的超共轭效应不如 $\rm O_2F_2$。故过氧键长度排序为 $\rm K_2O_2>\bf A>\rm O_2F_2$，说法5错误。

<Checkpoint>[$\rm O_2F_2$  中氧的孤对电子与另一氧氟键的反键轨道超共轭，增强过氧键键级](1)</Checkpoint>

<Checkpoint>[过氧键键长排序 $\rm K_2O_2>\bf A>\rm O_2F_2$](1)</Checkpoint>

正确的说法为2,3,4，答案为F选项。