How to align flexbox columns left and right?

You could add justify-content: space-between to the parent element. In doing so, the children flexbox items will be aligned to opposite sides with space between them.

Updated Example

#container {
    width: 500px;
    border: solid 1px #000;
    display: flex;
    justify-content: space-between;
}

#container {
    width: 500px;
    border: solid 1px #000;
    display: flex;
    justify-content: space-between;
}

#a {
    width: 20%;
    border: solid 1px #000;
}

#b {
    width: 20%;
    border: solid 1px #000;
    height: 200px;
}
<div id="container">
    <div id="a">
        a
    </div>
    <div id="b">
        b
    </div>
</div>

You could also add margin-left: auto to the second element in order to align it to the right.

Updated Example

#b {
    width: 20%;
    border: solid 1px #000;
    height: 200px;
    margin-left: auto;
}

#container {
    width: 500px;
    border: solid 1px #000;
    display: flex;
}

#a {
    width: 20%;
    border: solid 1px #000;
    margin-right: auto;
}

#b {
    width: 20%;
    border: solid 1px #000;
    height: 200px;
    margin-left: auto;
}
<div id="container">
    <div id="a">
        a
    </div>
    <div id="b">
        b
    </div>
</div>

I came up with 4 methods to achieve the results. Here is demo

Method 1:

#a {
    margin-right: auto;
}

Method 2:

#a {
    flex-grow: 1;
}

Method 3:

#b {
    margin-left: auto;
}

Method 4:

#container {
    justify-content: space-between;
}