无机盐工业 ›› 2021, Vol. 53 ›› Issue (1): 30-35.doi: 10.11962/1006-4990.2020-0103
收稿日期:
2020-07-11
出版日期:
2021-01-10
发布日期:
2021-01-08
通讯作者:
朱静
作者简介:
杨家敏(1994— ),女,硕士研究生,研究方向为化学工艺;E-mail: 基金资助:
Yang Jiamin(),Zhu Jing(),Hu Xue,Wu Qiang,Li Tianxiang
Received:
2020-07-11
Online:
2021-01-10
Published:
2021-01-08
Contact:
Zhu Jing
摘要:
采用等温溶解平衡法测定了283.15 K下KCl-NH4Cl-H2O和KH2PO4-NH4H2PO4-H2O两个三元体系的溶解度,采用X射线衍射法和湿渣法联合测定平衡固相结构和组成。结果表明,两个体系平衡固相均有部分互溶的固溶体产生,两个相图分别包含一个共饱和点、两条单变量曲线和6个区域。采用Pitzer模型关联和计算两个体系的溶解度数据,结果表明,KCl-NH4Cl-H2O体系的最大相对误差为3.096 9%,最小相对误差为0.038 3%,KH2PO4-NH4H2PO4-H2O体系的最大相对误差为5.935 6%,最小相对误差为0.069 8%,模型计算值与实验值基本一致。
中图分类号:
杨家敏,朱静,胡雪,吴强,李天祥. 283.15 K下三元KCl-NH4Cl-H2O和KH2PO4-NH4H2PO4-H2O体系固-液相平衡测定与关联[J]. 无机盐工业, 2021, 53(1): 30-35.
Yang Jiamin,Zhu Jing,Hu Xue,Wu Qiang,Li Tianxiang. Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH4Cl-H2O and KH2PO4-NH4H2PO4-H2O systems at 283.15 K[J]. Inorganic Chemicals Industry, 2021, 53(1): 30-35.
表2
在283.15 K下三元体系KCl-NH4Cl-H2O的固-液相平衡数据
序 号 | 液相组成/% | 湿固相/% | 平衡 固相 | ||||
---|---|---|---|---|---|---|---|
实验值 | Pitzer计算值 | ||||||
w (KCl) | w (NH4Cl) | w (KCl) | w (NH4Cl) | w (KCl) | w (NH4Cl) | ||
1,a | 23.69 | 0.00 | 23.67 | 0.00 | — | — | KCl |
2 | 22.46 | 1.67 | 22.36 | 1.77 | 91.19 | 1.17 | (K,NH4)Cl |
3 | 20.28 | 4.54 | 20.19 | 4.63 | 90.09 | 1.72 | (K,NH4)Cl |
4 | 16.81 | 8.65 | 17.04 | 8.42 | 88.56 | 3.18 | (K,NH4)Cl |
5 | 15.32 | 11.13 | 15.05 | 11.40 | 85.59 | 5.52 | (K,NH4)Cl |
6 | 13.90 | 13.48 | 13.81 | 13.57 | 81.03 | 7.94 | (K,NH4)Cl |
7 | 13.12 | 15.56 | 13.07 | 15.61 | 79.08 | 8.36 | (K,NH4)Cl |
8 | 11.77 | 17.96 | 11.95 | 17.78 | 78.03 | 10.63 | (K,NH4)Cl |
9,b | 11.54 | 18.63 | 11.42 | 18.75 | 63.01 | 19.44 | (K,NH4)Cl+(NH4,K)Cl |
10 | 11.48 | 19.29 | 11.48 | 19.29 | 13.10 | 64.69 | (NH4,K)Cl |
11 | 6.65 | 21.59 | 6.61 | 21.63 | 5.63 | 75.04 | (NH4,K)Cl |
12 | 2.33 | 23.80 | 2.38 | 23.75 | 3.97 | 72.98 | (NH4,K)Cl |
13,d | 0.00 | 24.68 | 0.00 | 24.67 | — | — | NH4Cl |
表3
在283.15 K下三元体系 KH2PO4-NH4H2PO4-H2O的固-液相平衡数据
序号 | 液相组成/% | 湿固相/% | 平衡固相 | ||||
---|---|---|---|---|---|---|---|
实验值 | Pitzer计算值 | ||||||
w(NH4H2PO4) | w(KH2PO4) | w(NH4H2PO4) | w(KH2PO4) | w(NH4H2PO4) | w(KH2PO4) | ||
1,a1 | 22.01 | 0.00 | 22.02 | 0.00 | — | — | NH4H2PO4 |
2 | 20.92 | 4.07 | 20.68 | 4.31 | 87.93 | 1.68 | (NH4,K)H2PO4 |
3 | 19.28 | 6.80 | 19.51 | 6.57 | 79.82 | 4.25 | (NH4,K)H2PO4 |
4 | 17.37 | 8.89 | 17.39 | 8.87 | 70.91 | 5.40 | (NH4,K)H2PO4 |
5 | 16.68 | 9.66 | 16.97 | 9.37 | 69.08 | 6.88 | (NH4,K)H2PO4 |
6,b1 | 15.32 | 10.43 | 15.11 | 10.64 | 60.98 | 12.65 | (NH4,K)H2PO4+(K,NH4)H2PO4 |
7 | 15.33 | 10.44 | 15.16 | 10.61 | 9.75 | 60.34 | (K,NH4)H2PO4 |
8 | 13.35 | 11.24 | 13.43 | 11.16 | 8.16 | 68.12 | (K,NH4)H2PO4 |
9 | 11.50 | 11.78 | 11.74 | 11.54 | 5.31 | 79.25 | (K,NH4)H2PO4 |
10 | 8.34 | 12.41 | 8.31 | 12.44 | 4.22 | 74.62 | (K,NH4)H2PO4 |
11 | 2.36 | 13.47 | 2.37 | 13.46 | 1.91 | 74.31 | (K,NH4)H2PO4 |
12,d1 | 0.00 | 15.47 | 0.00 | 15.46 | — | — | KH2PO4 |
表5
在283.15 K下三元体系KCl-NH4Cl-H2O的固-液相平衡实验数据和Pitzer模型计算值
序号 | 固溶体中NH4Cl的物质的量 分数/% | 液相组成 | 活度积 | |||||||
---|---|---|---|---|---|---|---|---|---|---|
实验值/(mol·kg-1) | Pitzer模型计算值/(mol·kg-1) | 相对误差/% | 实验值 | Pitzer模型计算值 | 相对 误差/% | |||||
m | m | m | m | m | m | |||||
1,a | 0 | 4.164 2 | 4.164 2 | 4.164 2 | 4.164 2 | 0 | 0 | 7.708 6 | 7.708 6 | 0 |
2 | 1.756 8 | 3.970 9 | 4.382 4 | 3.953 1 | 4.364 6 | 0.449 9 | 0.407 7 | 6.732 0 | 6.970 3 | 3.540 1 |
3 | 2.591 9 | 3.618 4 | 4.747 4 | 3.603 2 | 4.732 2 | 0.419 7 | 0.319 9 | 6.723 0 | 7.086 9 | 5.413 0 |
4 | 4.766 0 | 3.025 0 | 5.194 5 | 3.065 7 | 5.235 1 | 1.343 0 | 0.782 1 | 6.545 4 | 6.804 7 | 3.960 4 |
5 | 8.247 3 | 2.794 0 | 5.623 1 | 2.745 5 | 5.574 5 | 1.737 1 | 0.863 2 | 6.597 9 | 6.580 2 | 0.268 3 |
6 | 12.015 8 | 2.567 5 | 6.037 8 | 2.550 5 | 6.020 8 | 0.662 0 | 0.281 5 | 7.354 8 | 6.929 1 | 5.788 1 |
7 | 12.841 7 | 2.467 6 | 6.546 3 | 2.457 7 | 6.536 4 | 0.402 9 | 0.151 9 | 7.673 8 | 7.751 4 | 1.012 0 |
8 | 15.956 9 | 2.246 8 | 7.0250 | 2.281 4 | 7.059 5 | 1.539 1 | 0.492 2 | 8.363 5 | 8.277 0 | 1.034 0 |
9,b | 30.069 6 | 2.216 7 | 7.204 4 | 2.193 7 | 7.181 4 | 1.037 9 | 0.319 4 | 9.010 8 | 8.519 5 | 5.452 4 |
10 | 87.313 5 | 2.224 3 | 7.433 5 | 2.225 2 | 7.410 3 | 0.038 3 | 0.312 3 | 10.621 0 | 10.444 0 | 1.666 1 |
11 | 94.891 8 | 1.243 1 | 6.867 7 | 1.236 0 | 6.860 7 | 0.569 9 | 0.103 2 | 8.675 9 | 9.054 9 | 4.368 4 |
12 | 96.243 5 | 0.423 1 | 6.446 4 | 0.432 5 | 6.455 8 | 3.096 9 | 0.202 9 | 8.206 2 | 8.089 8 | 1.418 8 |
13,d | 100 | 0 | 6.225 1 | 0 | 6.225 1 | 0 | 0 | 14.154 0 | 14.154 0 | 0 |
表6
在283.15 K下三元体系 KH2PO4-NH4H2PO4-H2O的固-液相平衡实验数据和Pitzer模型计算值
序号 | 固溶体中NH4Cl的物质的量 分数/% | 液相组成 | 活度积 | |||||||
---|---|---|---|---|---|---|---|---|---|---|
实验值/(mol·kg-1) | Pitzer模型计算值/(mol·kg-1) | 相对误差/% | 实验值 | Pitzer模型计算值 | 相对 误差/% | |||||
m | m | m | m | m | m | |||||
1,a1 | 100 | 0 | 2.453 4 | 0 | 2.453 4 | 0 | 0 | 0.3864 | 0.386 4 | 0 |
2 | 86.082 9 | 0.398 7 | 2.823 3 | 0.422 4 | 2.846 9 | 5.935 6 | 0.838 2 | 0.322 8 | 0.325 0 | 0.678 2 |
3 | 77.334 2 | 0.676 0 | 2.943 4 | 0.652 9 | 2.920 4 | 3.405 8 | 0.782 1 | 0.299 8 | 0.300 3 | 0.176 6 |
4 | 70.160 4 | 0.885 9 | 2.933 7 | 0.883 8 | 2.931 6 | 0.231 0 | 0.069 8 | 0.287 3 | 0.287 7 | 0.125 0 |
5 | 67.510 1 | 0.963 6 | 2.932 2 | 0.935 1 | 2.903 7 | 2.965 4 | 0.974 6 | 0.281 5 | 0.281 9 | 0.165 8 |
6,b1 | 63.867 2 | 1.032 2 | 2.825 9 | 1.052 6 | 2.846 3 | 1.972 2 | 0.720 4 | 0.272 7 | 0.274 4 | 0.616 6 |
7 | 63.860 2 | 1.033 5 | 2.828 8 | 1.050 0 | 2.845 4 | 1.604 4 | 0.586 2 | 0.273 0 | 0.274 3 | 0.485 5 |
8 | 58.835 5 | 1.095 2 | 2.634 3 | 1.087 8 | 2.626 8 | 0.684 1 | 0.284 4 | 0.232 4 | 0.238 9 | 2.783 3 |
9 | 54.018 2 | 1.128 3 | 2.431 4 | 1.104 8 | 2.407 9 | 2.077 3 | 0.964 0 | 0.223 7 | 0.221 9 | 0.776 9 |
10 | 44.712 2 | 1.150 7 | 2.065 5 | 1.153 9 | 2.068 7 | 0.278 2 | 0.155 0 | 0.198 2 | 0.198 3 | 0.032 8 |
11 | 17.412 5 | 1.175 9 | 1.419 7 | 1.174 7 | 1.418 5 | 0.103 0 | 0.085 3 | 0.176 2 | 0.176 2 | 0.006 2 |
12 | 0 | 1.344 8 | 1.344 8 | 1.344 8 | 1.344 8 | 0 | 0 | 0.256 6 | 0.256 6 | 0 |
13,d1 | 100 | 0 | 2.453 4 | 0 | 2.453 4 | 0 | 0 | 0.386 4 | 0.386 4 | 0 |
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